Molecular complexes of group 13 element trihalides with pyridine … · 2013-06-12 · 1...
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1 Supplementary information Structural and thermodynamic properties of molecular complexes of aluminum and gallium trihalides with bifunctional donor pyrazine: decisive role of Lewis acidity on 1D polymer formation Tatiana N. Sevastianova, † Michael Bodensteiner, ‡ Anna S. Lisovenko, † Elena I. Davydova, † Manfred Scheer, ‡ Tatiana V. Susliakova, † Irina S. Krasnova, Alexey Y. Timoshkin †* † Inorganic Chemistry Group, Department of Chemistry, St. Petersburg State University, University Pr. 26, Old Peterhof, St. Petersburg, 198504, Russia. E-mail: [email protected] ‡ Department of Inorganic Chemistry, University of Regensburg, 93040 Regensburg, Germany, E- mail: [email protected] Study of the pyrolytic products of Al 2 Br 6 pyz. In conclusion of the tensimetry experiment 5 the system was kept at 415 ºC for 4 hours, and after the volatile compounds were separated (condensed into the compartment at room temperature upon heating of the system at 280-300 ºC for 36 hours) and analyzed by mass-spectrometry (170 ºC, 70 eV). Ions AlBr 2 pyz + (22%) and AlBr 3 pyz + (15%) indicate that some amount of the AlBr 3 ·pyz complex remained after pyrolysis. However, the most intensive ion signal AlBr 2 NH 3 + (100%) indicates the formation of an AlBr 3 NH 3 adduct. Presumably ammonia is generated via pyrolysis of pyrazine. Moreover, the detection of the ion AlBr 2 C 5 H 6 N 2 + (15%) may be assigned to a fragmentation upon ionization of the AlBr 3 - methylpyrazine complex. Its occurance suggests that the formation of methylated pyrazine occurs via Friedel-Crafts reactions in the melt, catalyzed by aluminum tribromide. Formation of methylated pyridine complexes was earlier observed via pyrolysis of GaCl 3 adduct with piperidine (A. S. Litvinenko, A. Y. Timoshkin and H. F. Schaefer, Polyhedron, 2006, 25, 2465). Electronic Supplementary Material (ESI) for Dalton Transactions This journal is © The Royal Society of Chemistry 2013
Transcript of Molecular complexes of group 13 element trihalides with pyridine … · 2013-06-12 · 1...
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Supplementary information
Structural and thermodynamic properties of molecular complexes of
aluminum and gallium trihalides with bifunctional donor pyrazine
decisive role of Lewis acidity on 1D polymer formation
Tatiana N Sevastianovadagger Michael Bodensteiner
Dagger Anna S Lisovenko
dagger Elena I Davydova
dagger
Manfred ScheerDagger Tatiana V Susliakova
dagger Irina S Krasnova Alexey Y Timoshkin
dagger
dagger Inorganic Chemistry Group Department of Chemistry St Petersburg State University University
Pr 26 Old Peterhof St Petersburg 198504 Russia E-mail alextimAT11692spbedu
Dagger Department of Inorganic Chemistry University of Regensburg 93040 Regensburg Germany E-
mail manfredscheerchemieuni-regensburgde
Study of the pyrolytic products of Al2Br6pyz In conclusion of the tensimetry experiment 5 the
system was kept at 415 ordmC for 4 hours and after the volatile compounds were separated (condensed
into the compartment at room temperature upon heating of the system at 280-300 ordmC for 36 hours)
and analyzed by mass-spectrometry (170 ordmC 70 eV) Ions AlBr2pyz+ (22) and AlBr3pyz
+ (15)
indicate that some amount of the AlBr3pyz complex remained after pyrolysis However the most
intensive ion signal AlBr2NH3+ (100) indicates the formation of an AlBr3NH3 adduct
Presumably ammonia is generated via pyrolysis of pyrazine Moreover the detection of the ion
AlBr2C5H6N2+ (15) may be assigned to a fragmentation upon ionization of the AlBr3-
methylpyrazine complex Its occurance suggests that the formation of methylated pyrazine occurs
via Friedel-Crafts reactions in the melt catalyzed by aluminum tribromide Formation of
methylated pyridine complexes was earlier observed via pyrolysis of GaCl3 adduct with piperidine
(A S Litvinenko A Y Timoshkin and H F Schaefer Polyhedron 2006 25 2465)
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Figure S1 Molecular structure of complex AlBr3middotpyzmiddotAlBr3 (1) in the crystal Selected interatomic
distances (Aring) Al1-N1 1999(6) Al1-Br1 22538(18) Al1-Br2 2267(2) Al1-Br3 22465(16)
Selected bond angles (deg) Br1-Al1-Br2 11340(6) Br1-Al1-Br3 11688(7) Br1-Al1-N1
10085(18) Br2-Al1-Br3 11467(9) Br2-Al1-N1 10443(16) Br3- Al1-N1 10417(15)
Figure S2 Molecular structure of complex GaCl3middotpyzmiddotGaCl3 (2) in the crystal Selected
interatomic distances (Aring) Ga1-N1 2044(7) Ga1-Cl1 2135(2) Ga1-Cl2 2147(2) Ga1-Cl3
2129(2) Selected bond angles (deg) Cl1- Ga1-Cl2 11299(8) Cl1-Ga1-Cl3 11686(8) Cl1-
Ga1-N1 1016(2) Cl2-Ga1-Cl3 11605(9) Cl2-Ga1-N1 10310(19) Cl3-Ga1- N1 10340(19)
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Figure S3 Molecular structure of complex (AlBr3middotpyz)infin (3) in the crystal Selected interatomic
distances (Aring) Al3-N1 2133(2) Al3-Br1 23099(15) Al3-Br2 23257(8) Selected bond angles
(deg) Br1-Al3-Br2 11595(3) Br1-Al3-N1 9342(8) Br2-Al3-N1 8638(7) Br2- Al3- Br2rsquo
12809(6) Br2-Al3-N1 9063(7) N1-Al3-N1 17316(13)
Figure S4 Molecular structure of complex (GaCl3middotpyz)infin (4) in the crystal Selected interatomic
distances (Aring) Ga1-N1 2203(5) Ga1-Cl1 21855(14) Ga1-Cl2 2174(2) Selected bond angles
(deg) Cl1-Ga1-Cl2 11732(4) Cl1-Ga1-N1 9050(12) Cl1-Ga1-Cl1 12536(6) Cl1- Ga1-N1
8751(12) Cl2-Ga1-N1 9216(12) N1-Ga1-N1 17568(17)
Figure S5 Molecular structure of complex GaI3middotpyz (5) in the crystal Selected interatomic
distances (Aring) Ga1-N1 2037(6) Ga1-I1 25137(10) Ga1-I2 25094(9) Ga1-I3 25081(11)
Selected bond angles (deg) I1-Ga1-I2 11657(4) I1-Ga1-I3 11209(4) I1-Ga1-N1 10254(16)
I2-Ga1-I3 11383(3) I2-Ga1-N1 10509(16) I3-Ga1-N1 10505(17)
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Table S1 Crystal Structure Information for investigated complexes
empiric formula C4H4Al2Br6N2 (1) C4H4Cl6Ga2N2 (2) C4H4AlBr3N2 (3) C4H4Cl3GaN2 (4) C4H4I3GaN2 (5)
Al2Br6pyz Ga2Cl6pyz (AlBr3pyz)infin (GaCl3pyz)infin GaI3pyz
Mr 61345 43223 34677 25616 53051
crystal size [mm] 032 times 013 times 006 049 times 032 times 023 060 times 025 times 018 013 times 002 times 002 043 times 020 times 020
T [K] 123(1) 123(1) 123(1) 123(1) 123(1)
[Aring] 154178 (Cu) 154178 (Cu) 071073 (Mo) 154178 (Cu) 071073 (Mo)
absorption correction type semi-empirical analytical analytical semi-empirical analytical
space group P21c P21c C2c C2c P
crystal system monoclinic monoclinic monoclinic monoclinic triclinic
a [Aring] 69688(3) 66265(7) 112325(11) 111474(7) 71493(10)
b [Aring] 158935(4) 154544(10) 67023(4) 63189(5) 93992(17)
c [Aring] 75060(3) 71401(8) 118372(19) 115922(8) 95165(12)
[deg] 90 90 90 90 60776(16)
[deg] 117596(5) 115721(13) 104753(14) 101953(7) 79488(12)
[deg] 90 90 90 90 87758(13)
V [Aring3] 73678(6) 65876(13) 86177(18) 79884(10) 54779(17)
Z 2 2 4 4 2
calcd [gcm3] 2765 2179 2673 2130 3216
[mmndash1
] 20616 15948 14072 13328 10908
range [deg] 557 ndash 6506 573 ndash 6668 356 ndash 3051 781 ndash 5892 346 ndash 2650
completeness to 0990 0985 0998 0989 0995
index range ndash7 le h le 6 ndash6 le h le 7 ndash 5 le h le 6 ndash 2 le h le ndash9 le h le 9
ndash 8 le k le 8 ndash 7 le k le 8 ndash7 le k le 9 ndash6le k le6 ndash 2 le k le 12
ndash8 le l le 8 ndash8 le l le 8 ndash 6 le l le 6 ndash 2le l le 2 ndash 2 le l le 2
unique reflections Igt 2 (Rint) 1056 (00713) 1088 (01356) 1027 (00426) 510 (00421) 2125 (0393)
datarestraintsparameters 1250064 1151064 1316048 565047 2573091
GOF in Fsup2 1040 1099 0986 1068 1025
R1wR2(Igt 2 (I)) 0035500841 0093602485 0032200762 0047301127 0040900789
R1wR2 (all data) 0044400877 0095702505 0046100795 0053601149 0055000863
largest diff [e Aring-3
] ndash10140910 ndash25321566 ndash07691265 ndash07721212 ndash14361358
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(a) (b)
(c) (d)
Figure S6 Structures of pyrazine complexes theoretically considered in the present work on the
example of gallium trihalide complexes (a) GaCl3middotpyz (b) (GaCl3)2middotpyz (c) GaCl3middot2pyz (d)
(GaCl3)2middot(pyz)3
N1
Cl3Cl2
Cl1
Cl6Cl5
Ga2N2Ga1
Cl4
N1
Cl3
Cl2
Cl1
Ga1
N1
Cl3
Cl2Cl1
Ga1
N1
Cl3Cl2
Cl1
Cl6
Cl5
Ga2N2
Ga1
Cl4
N3N4
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Table S2 Comparison of theoretically predicted and experimental bond distances (in angstroms)
and bond angles (in degrees)
Compound Method rM-N rM-Х ltN-M-X ltX-M-X
AlCl3∙pyz B3LYP 2028 2134-2138 1019-1028 1151-1162
AlCl3∙pyzAlCl3 B3LYP 2063 21262131 1002-1016 1159-1172
pyz∙AlCl3∙pyz B3LYP 2182 2187 878-922 1195-1210
pyz∙AlCl3∙pyz∙AlCl3∙pyz B3LYP 21632228 2181-2182 880-929 1190-1204
AlBr3∙pyz B3LYP 2037 2299-2303 1016-1038 1150-1156
AlBr3∙pyzAlBr3 B3LYP 2074 2292-2295 999-1027 1158-1166
AlBr3∙pyzAlBr3 (1) X-ray 1999 2247-2267 10085-10443 1134-1169
pyz∙AlBr3∙pyz B3LYP 2208 2359-2361 874-930 1197-1205
pyz∙AlBr3∙pyz∙AlBr3∙pyz B3LYP 2182 2259 2352-2355 884-896 1198-1203
(AlBr3∙pyz)infin (3) X-ray 2133 2310-2326 864-934 1160-1281
AlI3∙pyz B3LYP 2053 2530-2534 1011-1043 1148-1152
AlI3∙pyzAlI3 B3LYP 2090 2522-2526 996-1035 1157-1162
pyz∙AlI3∙pyz B3LYP 2242 2244 2594-2603 867-940 1150-1226
pyz∙AlI3∙pyz∙AlI3∙pyz B3LYP 2215 2330 2586-2591 864-953 1184-1207
GaCl3∙pyz B3LYP 2096 2180-2184 1016-1018 1155-1171
GaCl3∙pyzGaCl3 B3LYP 2141 2173-2177 1000-1004 1163-1180
GaCl3∙pyzGaCl3 (2) X-ray 2044 2135-2147 1016-1034 1130-1169
pyz∙GaCl3∙pyz B3LYP 2276 2223-2224 881-919 1196-1208
pyz∙GaCl3∙pyz∙GaCl3∙pyz B3LYP 2243 2336 2218-2219 867-934 1192-1203
(GaCl3∙pyz)infin (4) X-ray 2203 2174-2186 875-9216 1173-1254
GaBr3∙pyz B3LYP 2113 2334-2337 1011-1026 1154-1165
GaBr3∙pyzGaBr3 B3LYP 2161 2327-2330 994-1014 1162-1175
pyz∙GaBr3∙pyz B3LYP 2326 2377-2378 877-925 1197-1206
pyz∙GaBr3∙pyz∙GaBr3∙pyz B3LYP 2277 2416 2371-2373 859-942 1193-1204
GaI3pyz B3LYP 2143 2551-2553 1004-1027 1157-1161
GaI3pyz (5) X-ray 2027 2504-2509 1026-1051 1121-1167
GaI3∙pyzGaI3 B3LYP 2193 2542-2547 992-1013 1167
pyz∙GaI3∙pyz B3LYP 2424 2425 2586-2589 876-931 1200
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Table S3 Total energies Eordm0 standard enthalpies Hordm298 (in Hartree) and entropies Sordm298 (in
cal mol-1
K-1
) B3LYPTZVP level of theory
Compound Eordm0 Hordm298 Sordm298
AlCl3∙Py -18717591724 -18716513100 108239
AlCl3∙pyz -18877870231 -18876915220 108056
AlCl3∙pyzAlCl3 -35111580608 -35110489670 148691
AlCl3(pyz)2 -21522048075 -21520251440 136595
(AlCl3)2(pyz)3 -40400023628 -40397248410 209795
AlBr3∙Py -82136228039 -82135155080 115781
AlBr3∙pyz -82296506985 -82295557760 115627
AlBr3∙pyzAlBr3 -161948858137 -161947779010 163708
AlBr3(pyz)2 -84940643503 -84938853240 146622
(AlBr3)2(pyz)3 -167237224514 -167234462290 225077
AlI3∙Py -13844590963 -1384352177 121837
AlI3∙pyz -14004871976 -1400392624 124387
AlI3∙pyzAlI3 -25365599319 -2536452716 175051
AlI3(pyz)2 -16648951507 -1664716600 151946
(AlI3)2(pyz)3 -30653841482 -3065108822 233288
GaCl3∙Py -35541541594 -3554046971 111664
GaCl3∙pyz -3570182340 -3570087489 111512
GaCl3∙pyzGaCl3 -6875949899 -6875842102 156295
GaCl3(pyz)2 -3834596631 -3834417720 141855
(GaCl3)2(pyz)3 -7404787740 -7404511645 217400
GaBr3∙Py -98960303362 -98959236330 119336
GaBr3∙pyz -99120587356 -99119643780 119266
GaBr3∙pyzGaBr3 -195597035548 -195595967440 171477
GaBr3(pyz)2 -101764685552 -101762902200 151269
(GaBr3)2(pyz)3 -200885318973 -200882569600 235047
GaI3Py -30668807732 -3066774365 126040
GaI3pyz -30829096463 -3082815563 126682
GaI3∙pyzGaI3 -59014069503 -5901300666 181996
GaI3(pyz)2 -3347313909 -3347136003 159749
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Table S4 BSSE energies kJ mol-1
B3LYPTZVP level of theory
Compound X=Cl X=Br X=I
AlX3py 74 62 45
AlX3pyz 74 61 38
AlX3∙pyzAlX3 146 123 99
AlX3(pyz)2 113 91 57
(AlX3)2(pyz)3 222 183 135
GaX3py 64 54 39
GaX3pyz 62 52 39
GaX3∙pyzGaX3 119 102 78
GaX3(pyz)2 89 73 52
(GaX3)2(pyz)3 181 151 -
Table S5 Structural and energetic parameters of mixed 21 complexes Standard
dissociation enthalpies ΔdissHordm298 kJ mol-1
and standard dissociation entropies ΔdissSordm298 J mol-1
K-1
B3LYPTZVP level of theory
MX3-pyz-MX3 r(N1-M) r(N2-M) ΔdissHordm298 ΔdissSordm298
AlCl3-pyz-GaCl3 2061 2144 1995 2769
AlCl3-pyz-AlBr3 2062 2075 2130 2821
AlCl3-pyz-GaBr3 2059 2167 1877 2787
GaCl3-pyz-AlBr3 2143 2072 1897 2817
GaCl3-pyz-GaBr3 2138 2164 1643 2778
AlBr3-pyz-GaBr3 2070 2166 1779 2829
Table S6 Summary of the tensimetry experiments performed in the AlBr3-pyz system
Experiment
number
Temperature
range K
Number of
heatingcooling runs
AlBr3pyz
ratio
Chemical composition (mass of
the substance in mg)
Volume
ml
1 291-675 3 11 AlBr3pyz (362) 2740
2 293-649 4 11 AlBr3pyz (455) 3337
3 291-660 3 1303 AlBr3pyz (455) pyz (213) 3060
4 5 21 (AlBr3)2pyz (282) 5550
5 12 2031 AlBr3 (514) pyz (76) 5905
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Table S7 Melting points Energies of the M-N bonds EM-N and melting enthalpies ΔmeltH kJ mol-1
Compound EM-N Tmelt K ΔmeltH
(AlBr3pyz)infin (3) 85 540 643b
(GaCl3pyz)infin (4) 77 461-463 [11]a 470 [12] 127 [12]
b
(GaBr3pyz)infin 64 361-363 [11]a
a synthesis in nonaqueous solutions
b estimated as difference between sublimation and vaporization
enthalpies from tensimetry studies
Figure S7 System for synthesis of complexes 1 2 3 and 4 ndash places for the sealing off А ndash
ampoule with known amount of pyrazine B ndash ampoule with known amount of AlBr3 С ndash
compartment for the introduction of pyz D ndash ampoule for removal of the excess component E ndash
reaction volume F ndash ampoule to remove the synthesized complex G ndash capillary for the mass
spectrometry study
E
Zeolites
To vacuum pump
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Figure S8 Optimized structures and xyz coordinates for considered aluminum compounds
B3LYPTZVP level of theory
X Y Z
N -1377 0012 -0093
C -0683 1157 -0096
C 0702 1145 -0097
N 1377 -0011 -0093
C 0683 -1157 -0096
C -0702 -1145 -0097
H -1248 2080 -0108
H 1279 2060 -0113
H 1248 -2079 -0108
H -1278 -2060 -0112
Al 3437 -0001 0008
Cl 3710 0310 2094
Cl 3911 -1943 -0731
Cl 3895 1657 -1249
Al -3438 0001 0008
Cl -3895 -1654 -1252
Cl -3710 -0314 2093
Cl -3911 1945 -0727
X Y Z
N 3671 0002 -0002
C 2969 -1130 -0018
C 1582 -1142 -0050
N 0895 0011 -0063
C 1589 1159 -0050
C 2977 1138 -0019
H 3524 -2061 -0008
H 1009 -2059 -0075
H 1020 2079 -0074
H 3537 2065 -0009
Al -1131 0001 0002
Cl -1502 -0192 2095
Cl -1643 1895 -0845
Cl -1622 -1719 -1167
X Y Z
C -3663 0001 0000
C -2962 1200 -0018
C -1579 1169 -0053
N -0895 0010 -0067
C -1572 -1153 -0054
C -2954 -1194 -0019
H -3473 2153 -0008
H -0985 2072 -0077
H -0973 -2054 -0080
H -3458 -2150 -0010
H -4746 -0003 0026
Al 1113 0001 0002
Cl 1517 -0174 2095
Cl 1639 -1726 -1149
Cl 1656 1886 -0859
a) AlCl Py3middot
b) AlCl pyz3middot
c) AlCl pyz AlCl3 3middot middot
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X Y Z
N -4969 0006 -0030
C -4247 0810 0750
C -2861 0771 0775
N -2181 -0091 0006
C -2896 -0902 -0781
C -4285 -0844 -0791
H -4786 1510 1378
H -2284 1423 1416
H -2345 -1599 -1396
H -4854 -1507 -1432
Al 0000 0000 0006
Cl 0000 0000 2193
Cl 0164 -1897 -1071
Cl -0164 1897 -1071
N 2181 0091 0007
C 2896 0902 -0781
C 4285 0844 -0791
N 4969 -0006 -0030
C 4247 -0810 0750C 2861 -0771 0775
H 2345 1599 -1396
H 4854 1507 -1432
H 4786 -1511 1378
H 2284 -1423 1416
d) AlCl (pyz)3 2
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X Y Z
N 0000 -1390 0313
C 0000 -0695 1451
C 0000 0695 1451
N 0000 1390 0313
C 0000 0691 -0830
C 0000 -0691 -0830
H 0000 -1258 2374
H 0000 1258 2374
H 0000 1249 -1755
H 0000 -1249 -1755
Al 0000 3614 0169
Cl 1880 3466 -0928
Cl -1880 3466 -0928
Cl 0000 3798 2342
Al 0000 -3614 0169
Cl -1880 -3466 -0928
Cl 1880 -3466 -0928
Cl 0000 -3798 2342
N 0000 -5757 -0124C 0000 -6214 -1385
C 0000 -7574 -1652N 0000 -8490 -0683
C 0000 -8029 0564C 0000 -6669 0855
H 0000 -5480 -2178H 0000 -7932 -2675
H 0000 -8758 1365
H 0000 -6298 1870N 0000 5757 -0124
C 0000 6669 0855C 0000 8029 0564
N 0000 8490 -0683C 0000 7574 -1652
C 0000 6214 -1385H 0000 6298 1870
H 0000 8758 1365H 0000 7932 -2675
H 0000 5480 -2178
e) (AlCl ) (pyz)3 2 3
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X Y Z
N -1379 0020 -0102
C -0677 1160 -0103
C 0709 1140 -0105
N 1379 -0020 -0102
C 0677 -1160 -0103
C -0709 -1140 -0105
H -1235 2087 -0110
H 1287 2053 -0119
H 1235 -2087 -0110
H -1287 -2053 -0119
Al 3450 0002 -0008
Br 3740 0589 2188
Br 4004 -2153 -0570
Br 3945 1626 -1551
Al -3450 -0002 -0008
Br -3945 -1626 -1551
Br -3740 -0589 2188
Br -4004 2154 -0570
X Y Z
C -4242 0080 -0114
C -3526 1271 -0114
C -2143 1223 -0113
N -1471 0057 -0111
C -2164 -1098 -0113
C -3546 -1123 -0113
H -4026 2230 -0117
H -1539 2120 -0119
H -1577 -2007 -0122
H -4062 -2074 -0116
H -5325 0089 -0116
Al 0541 -0001 0004
Br 0905 -0462 2232
Br 1115 -1718 -1426
Br 1224 2097 -0672
f) AlBr Py3middot
g) AlBr pyz3middot
h) AlBr pyz AlBr3 3middot middot
X Y Z
N 4244 0081 -0125
C 3556 -1060 -0119
C 2169 -1090 -0114
N 1466 0054 -0112
C 2146 1211 -0119
C 3534 1208 -0125
H 4123 -1983 -0121
H 1610 -2016 -0119
H 1565 2123 -0126
H 4082 2142 -0132
Al -0567 -0003 0007
Br -0887 -0431 2243
Br -1216 2091 -0699
Br -1109 -1740 -1402
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X Y Z
N -4996 -0097 0013
C -4277 0761 0737
C -2890 0750 0739
N -2204 -0137 0005
C -2917 -1000 -0728
C -4307 -0970 -0716
H -4819 1482 1338
H -2320 1449 1334
H -2364 -1716 -1319
H -4872 -1676 -1314
Al 0000 0000 -0012
Br 0000 0000 2348
Br 0243 -2033 -1182
Br -0243 2033 -1182
N 2204 0137 0005
C 2917 1000 -0728
C 4307 0970 -0716
N 4996 0097 0013
C 4277 -0761 0737C 2890 -0750 0739
H 2364 1716 -1319H 4872 1676 -1314
H 4819 -1482 1338H 2320 -1449 1334
i) AlBr (pyz)3 2
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X Y Z
N -1391 0048 -0040
C -0646 0600 -1003
C 0739 0552 -0962
N 1391 -0048 0040
C 0646 -0600 1003
C -0739 -0552 0962
H -1169 1088 -1813
H 1332 0999 -1747
H 1169 -1087 1813
H -1332 -0999 1747
Al 3649 0031 0042
Br 3785 -1446 1868
Br 3615 -0823 -2153
Br 3424 2342 0420
Al -3649 -0031 -0042
Br -3424 -2342 -0421
Br -3615 0822 2153
Br -3785 1446 -1867
N -5829 -0094 0032
C -6572 -1191 -0152
C -7961 -1130 -0096
N -8617 0003 0138
C -7867 1090 0320
C -6482 1054 0269
H -6046 -2115 -0341
H -8551 -2026 -0247
H -8382 2024 0513
H -5887 1943 0421
N 5829 0094 -0032
C 6572 1191 0151
C 7961 1130 0096
N 8617 -0003 -0138
C 7867 -1091 -0320
C 6482 -1054 -0269
H 6046 2115 0341
H 8552 2026 0247
H 8382 -2024 -0513
H 5887 -1943 -0420
j) (AlBr ) (pyz)3 2 3
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X Y Z
N 1382 -0013 -0121
C 0682 -1156 -0119
C -0703 -1142 -0120
N -1382 0013 -0121
C -0682 1156 -0119
C 0703 1142 -0120
H 1241 -2082 -0128
H -1277 -2059 -0134
H -1241 2082 -0128
H 1277 2059 -0134
Al -3470 -0006 -0020
I -3767 -0416 2451
I -4124 2286 -0857
I -4054 -1937 -1541
Al 3470 0006 -0020
I 4054 1937 -1541
I 3767 0416 2451
I 4124 -2286 -0857
X Y Z
N -1808 -0040 0000
Al 0220 0038 0000
I 0828 -1193 2134
I 0828 2503 0000
I 0828 -1193 -2134
C -4570 -0274 0000
C -2392 -1255 0000
C -2585 1057 0000
C -3967 0977 0000
C -3765 -1408 0000
H -1727 -2108 0000
H -2066 2007 0000
H -4553 1886 0000
H -4189 -2403 0000
H -5649 -0366 0000
X Y Z
N -4439 0000 -1124
C -3756 1133 -0975
C -2400 1149 -0679
N -1722 0000 -0532
C -2400 -1149 -0679
C -3756 -1133 -0975
H -4299 2063 -1094
H -1843 2070 -0567
H -1843 -2070 -0567
H -4299 -2063 -1094
Al 0249 0000 0041
I 0022 0000 2561
I 1178 -2136 -0957
I 1178 2136 -0957
k) AlI Py3middot
l) AlI pyz3middot
m) AlI pyz AlI3 3middot middot
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X Y Z
N -5010 0212 -0396
C -4286 -0860 -0720
C -2910 -0902 -0560
N -2236 0146 -0063
C -2954 1226 0263
C -4335 1248 0092
H -4816 -1716 -1121
H -2338 -1779 -0827
H -2416 2073 0664
H -4902 2132 0361
Al 0000 0000 0059
I 0000 0000 -2545
I 0252 2176 1448
I -0252 -2176 1448
N 2236 -0146 -0063
C 2954 -1226 0263
C 4335 -1248 0092
N 5010 -0212 -0396
C 4286 0860 -0720
C 2910 0902 -0560
H 2416 -2073 0664
H 4902 -2132 0361
H 4816 1716 -1121
H 2338 1779 -0827
n) AlI (pyz)3 2
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o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
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Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
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d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
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e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
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f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
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i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
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j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
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X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
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n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
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Figure S1 Molecular structure of complex AlBr3middotpyzmiddotAlBr3 (1) in the crystal Selected interatomic
distances (Aring) Al1-N1 1999(6) Al1-Br1 22538(18) Al1-Br2 2267(2) Al1-Br3 22465(16)
Selected bond angles (deg) Br1-Al1-Br2 11340(6) Br1-Al1-Br3 11688(7) Br1-Al1-N1
10085(18) Br2-Al1-Br3 11467(9) Br2-Al1-N1 10443(16) Br3- Al1-N1 10417(15)
Figure S2 Molecular structure of complex GaCl3middotpyzmiddotGaCl3 (2) in the crystal Selected
interatomic distances (Aring) Ga1-N1 2044(7) Ga1-Cl1 2135(2) Ga1-Cl2 2147(2) Ga1-Cl3
2129(2) Selected bond angles (deg) Cl1- Ga1-Cl2 11299(8) Cl1-Ga1-Cl3 11686(8) Cl1-
Ga1-N1 1016(2) Cl2-Ga1-Cl3 11605(9) Cl2-Ga1-N1 10310(19) Cl3-Ga1- N1 10340(19)
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Figure S3 Molecular structure of complex (AlBr3middotpyz)infin (3) in the crystal Selected interatomic
distances (Aring) Al3-N1 2133(2) Al3-Br1 23099(15) Al3-Br2 23257(8) Selected bond angles
(deg) Br1-Al3-Br2 11595(3) Br1-Al3-N1 9342(8) Br2-Al3-N1 8638(7) Br2- Al3- Br2rsquo
12809(6) Br2-Al3-N1 9063(7) N1-Al3-N1 17316(13)
Figure S4 Molecular structure of complex (GaCl3middotpyz)infin (4) in the crystal Selected interatomic
distances (Aring) Ga1-N1 2203(5) Ga1-Cl1 21855(14) Ga1-Cl2 2174(2) Selected bond angles
(deg) Cl1-Ga1-Cl2 11732(4) Cl1-Ga1-N1 9050(12) Cl1-Ga1-Cl1 12536(6) Cl1- Ga1-N1
8751(12) Cl2-Ga1-N1 9216(12) N1-Ga1-N1 17568(17)
Figure S5 Molecular structure of complex GaI3middotpyz (5) in the crystal Selected interatomic
distances (Aring) Ga1-N1 2037(6) Ga1-I1 25137(10) Ga1-I2 25094(9) Ga1-I3 25081(11)
Selected bond angles (deg) I1-Ga1-I2 11657(4) I1-Ga1-I3 11209(4) I1-Ga1-N1 10254(16)
I2-Ga1-I3 11383(3) I2-Ga1-N1 10509(16) I3-Ga1-N1 10505(17)
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Table S1 Crystal Structure Information for investigated complexes
empiric formula C4H4Al2Br6N2 (1) C4H4Cl6Ga2N2 (2) C4H4AlBr3N2 (3) C4H4Cl3GaN2 (4) C4H4I3GaN2 (5)
Al2Br6pyz Ga2Cl6pyz (AlBr3pyz)infin (GaCl3pyz)infin GaI3pyz
Mr 61345 43223 34677 25616 53051
crystal size [mm] 032 times 013 times 006 049 times 032 times 023 060 times 025 times 018 013 times 002 times 002 043 times 020 times 020
T [K] 123(1) 123(1) 123(1) 123(1) 123(1)
[Aring] 154178 (Cu) 154178 (Cu) 071073 (Mo) 154178 (Cu) 071073 (Mo)
absorption correction type semi-empirical analytical analytical semi-empirical analytical
space group P21c P21c C2c C2c P
crystal system monoclinic monoclinic monoclinic monoclinic triclinic
a [Aring] 69688(3) 66265(7) 112325(11) 111474(7) 71493(10)
b [Aring] 158935(4) 154544(10) 67023(4) 63189(5) 93992(17)
c [Aring] 75060(3) 71401(8) 118372(19) 115922(8) 95165(12)
[deg] 90 90 90 90 60776(16)
[deg] 117596(5) 115721(13) 104753(14) 101953(7) 79488(12)
[deg] 90 90 90 90 87758(13)
V [Aring3] 73678(6) 65876(13) 86177(18) 79884(10) 54779(17)
Z 2 2 4 4 2
calcd [gcm3] 2765 2179 2673 2130 3216
[mmndash1
] 20616 15948 14072 13328 10908
range [deg] 557 ndash 6506 573 ndash 6668 356 ndash 3051 781 ndash 5892 346 ndash 2650
completeness to 0990 0985 0998 0989 0995
index range ndash7 le h le 6 ndash6 le h le 7 ndash 5 le h le 6 ndash 2 le h le ndash9 le h le 9
ndash 8 le k le 8 ndash 7 le k le 8 ndash7 le k le 9 ndash6le k le6 ndash 2 le k le 12
ndash8 le l le 8 ndash8 le l le 8 ndash 6 le l le 6 ndash 2le l le 2 ndash 2 le l le 2
unique reflections Igt 2 (Rint) 1056 (00713) 1088 (01356) 1027 (00426) 510 (00421) 2125 (0393)
datarestraintsparameters 1250064 1151064 1316048 565047 2573091
GOF in Fsup2 1040 1099 0986 1068 1025
R1wR2(Igt 2 (I)) 0035500841 0093602485 0032200762 0047301127 0040900789
R1wR2 (all data) 0044400877 0095702505 0046100795 0053601149 0055000863
largest diff [e Aring-3
] ndash10140910 ndash25321566 ndash07691265 ndash07721212 ndash14361358
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(a) (b)
(c) (d)
Figure S6 Structures of pyrazine complexes theoretically considered in the present work on the
example of gallium trihalide complexes (a) GaCl3middotpyz (b) (GaCl3)2middotpyz (c) GaCl3middot2pyz (d)
(GaCl3)2middot(pyz)3
N1
Cl3Cl2
Cl1
Cl6Cl5
Ga2N2Ga1
Cl4
N1
Cl3
Cl2
Cl1
Ga1
N1
Cl3
Cl2Cl1
Ga1
N1
Cl3Cl2
Cl1
Cl6
Cl5
Ga2N2
Ga1
Cl4
N3N4
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Table S2 Comparison of theoretically predicted and experimental bond distances (in angstroms)
and bond angles (in degrees)
Compound Method rM-N rM-Х ltN-M-X ltX-M-X
AlCl3∙pyz B3LYP 2028 2134-2138 1019-1028 1151-1162
AlCl3∙pyzAlCl3 B3LYP 2063 21262131 1002-1016 1159-1172
pyz∙AlCl3∙pyz B3LYP 2182 2187 878-922 1195-1210
pyz∙AlCl3∙pyz∙AlCl3∙pyz B3LYP 21632228 2181-2182 880-929 1190-1204
AlBr3∙pyz B3LYP 2037 2299-2303 1016-1038 1150-1156
AlBr3∙pyzAlBr3 B3LYP 2074 2292-2295 999-1027 1158-1166
AlBr3∙pyzAlBr3 (1) X-ray 1999 2247-2267 10085-10443 1134-1169
pyz∙AlBr3∙pyz B3LYP 2208 2359-2361 874-930 1197-1205
pyz∙AlBr3∙pyz∙AlBr3∙pyz B3LYP 2182 2259 2352-2355 884-896 1198-1203
(AlBr3∙pyz)infin (3) X-ray 2133 2310-2326 864-934 1160-1281
AlI3∙pyz B3LYP 2053 2530-2534 1011-1043 1148-1152
AlI3∙pyzAlI3 B3LYP 2090 2522-2526 996-1035 1157-1162
pyz∙AlI3∙pyz B3LYP 2242 2244 2594-2603 867-940 1150-1226
pyz∙AlI3∙pyz∙AlI3∙pyz B3LYP 2215 2330 2586-2591 864-953 1184-1207
GaCl3∙pyz B3LYP 2096 2180-2184 1016-1018 1155-1171
GaCl3∙pyzGaCl3 B3LYP 2141 2173-2177 1000-1004 1163-1180
GaCl3∙pyzGaCl3 (2) X-ray 2044 2135-2147 1016-1034 1130-1169
pyz∙GaCl3∙pyz B3LYP 2276 2223-2224 881-919 1196-1208
pyz∙GaCl3∙pyz∙GaCl3∙pyz B3LYP 2243 2336 2218-2219 867-934 1192-1203
(GaCl3∙pyz)infin (4) X-ray 2203 2174-2186 875-9216 1173-1254
GaBr3∙pyz B3LYP 2113 2334-2337 1011-1026 1154-1165
GaBr3∙pyzGaBr3 B3LYP 2161 2327-2330 994-1014 1162-1175
pyz∙GaBr3∙pyz B3LYP 2326 2377-2378 877-925 1197-1206
pyz∙GaBr3∙pyz∙GaBr3∙pyz B3LYP 2277 2416 2371-2373 859-942 1193-1204
GaI3pyz B3LYP 2143 2551-2553 1004-1027 1157-1161
GaI3pyz (5) X-ray 2027 2504-2509 1026-1051 1121-1167
GaI3∙pyzGaI3 B3LYP 2193 2542-2547 992-1013 1167
pyz∙GaI3∙pyz B3LYP 2424 2425 2586-2589 876-931 1200
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Table S3 Total energies Eordm0 standard enthalpies Hordm298 (in Hartree) and entropies Sordm298 (in
cal mol-1
K-1
) B3LYPTZVP level of theory
Compound Eordm0 Hordm298 Sordm298
AlCl3∙Py -18717591724 -18716513100 108239
AlCl3∙pyz -18877870231 -18876915220 108056
AlCl3∙pyzAlCl3 -35111580608 -35110489670 148691
AlCl3(pyz)2 -21522048075 -21520251440 136595
(AlCl3)2(pyz)3 -40400023628 -40397248410 209795
AlBr3∙Py -82136228039 -82135155080 115781
AlBr3∙pyz -82296506985 -82295557760 115627
AlBr3∙pyzAlBr3 -161948858137 -161947779010 163708
AlBr3(pyz)2 -84940643503 -84938853240 146622
(AlBr3)2(pyz)3 -167237224514 -167234462290 225077
AlI3∙Py -13844590963 -1384352177 121837
AlI3∙pyz -14004871976 -1400392624 124387
AlI3∙pyzAlI3 -25365599319 -2536452716 175051
AlI3(pyz)2 -16648951507 -1664716600 151946
(AlI3)2(pyz)3 -30653841482 -3065108822 233288
GaCl3∙Py -35541541594 -3554046971 111664
GaCl3∙pyz -3570182340 -3570087489 111512
GaCl3∙pyzGaCl3 -6875949899 -6875842102 156295
GaCl3(pyz)2 -3834596631 -3834417720 141855
(GaCl3)2(pyz)3 -7404787740 -7404511645 217400
GaBr3∙Py -98960303362 -98959236330 119336
GaBr3∙pyz -99120587356 -99119643780 119266
GaBr3∙pyzGaBr3 -195597035548 -195595967440 171477
GaBr3(pyz)2 -101764685552 -101762902200 151269
(GaBr3)2(pyz)3 -200885318973 -200882569600 235047
GaI3Py -30668807732 -3066774365 126040
GaI3pyz -30829096463 -3082815563 126682
GaI3∙pyzGaI3 -59014069503 -5901300666 181996
GaI3(pyz)2 -3347313909 -3347136003 159749
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S8
Table S4 BSSE energies kJ mol-1
B3LYPTZVP level of theory
Compound X=Cl X=Br X=I
AlX3py 74 62 45
AlX3pyz 74 61 38
AlX3∙pyzAlX3 146 123 99
AlX3(pyz)2 113 91 57
(AlX3)2(pyz)3 222 183 135
GaX3py 64 54 39
GaX3pyz 62 52 39
GaX3∙pyzGaX3 119 102 78
GaX3(pyz)2 89 73 52
(GaX3)2(pyz)3 181 151 -
Table S5 Structural and energetic parameters of mixed 21 complexes Standard
dissociation enthalpies ΔdissHordm298 kJ mol-1
and standard dissociation entropies ΔdissSordm298 J mol-1
K-1
B3LYPTZVP level of theory
MX3-pyz-MX3 r(N1-M) r(N2-M) ΔdissHordm298 ΔdissSordm298
AlCl3-pyz-GaCl3 2061 2144 1995 2769
AlCl3-pyz-AlBr3 2062 2075 2130 2821
AlCl3-pyz-GaBr3 2059 2167 1877 2787
GaCl3-pyz-AlBr3 2143 2072 1897 2817
GaCl3-pyz-GaBr3 2138 2164 1643 2778
AlBr3-pyz-GaBr3 2070 2166 1779 2829
Table S6 Summary of the tensimetry experiments performed in the AlBr3-pyz system
Experiment
number
Temperature
range K
Number of
heatingcooling runs
AlBr3pyz
ratio
Chemical composition (mass of
the substance in mg)
Volume
ml
1 291-675 3 11 AlBr3pyz (362) 2740
2 293-649 4 11 AlBr3pyz (455) 3337
3 291-660 3 1303 AlBr3pyz (455) pyz (213) 3060
4 5 21 (AlBr3)2pyz (282) 5550
5 12 2031 AlBr3 (514) pyz (76) 5905
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S9
Table S7 Melting points Energies of the M-N bonds EM-N and melting enthalpies ΔmeltH kJ mol-1
Compound EM-N Tmelt K ΔmeltH
(AlBr3pyz)infin (3) 85 540 643b
(GaCl3pyz)infin (4) 77 461-463 [11]a 470 [12] 127 [12]
b
(GaBr3pyz)infin 64 361-363 [11]a
a synthesis in nonaqueous solutions
b estimated as difference between sublimation and vaporization
enthalpies from tensimetry studies
Figure S7 System for synthesis of complexes 1 2 3 and 4 ndash places for the sealing off А ndash
ampoule with known amount of pyrazine B ndash ampoule with known amount of AlBr3 С ndash
compartment for the introduction of pyz D ndash ampoule for removal of the excess component E ndash
reaction volume F ndash ampoule to remove the synthesized complex G ndash capillary for the mass
spectrometry study
E
Zeolites
To vacuum pump
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S10
Figure S8 Optimized structures and xyz coordinates for considered aluminum compounds
B3LYPTZVP level of theory
X Y Z
N -1377 0012 -0093
C -0683 1157 -0096
C 0702 1145 -0097
N 1377 -0011 -0093
C 0683 -1157 -0096
C -0702 -1145 -0097
H -1248 2080 -0108
H 1279 2060 -0113
H 1248 -2079 -0108
H -1278 -2060 -0112
Al 3437 -0001 0008
Cl 3710 0310 2094
Cl 3911 -1943 -0731
Cl 3895 1657 -1249
Al -3438 0001 0008
Cl -3895 -1654 -1252
Cl -3710 -0314 2093
Cl -3911 1945 -0727
X Y Z
N 3671 0002 -0002
C 2969 -1130 -0018
C 1582 -1142 -0050
N 0895 0011 -0063
C 1589 1159 -0050
C 2977 1138 -0019
H 3524 -2061 -0008
H 1009 -2059 -0075
H 1020 2079 -0074
H 3537 2065 -0009
Al -1131 0001 0002
Cl -1502 -0192 2095
Cl -1643 1895 -0845
Cl -1622 -1719 -1167
X Y Z
C -3663 0001 0000
C -2962 1200 -0018
C -1579 1169 -0053
N -0895 0010 -0067
C -1572 -1153 -0054
C -2954 -1194 -0019
H -3473 2153 -0008
H -0985 2072 -0077
H -0973 -2054 -0080
H -3458 -2150 -0010
H -4746 -0003 0026
Al 1113 0001 0002
Cl 1517 -0174 2095
Cl 1639 -1726 -1149
Cl 1656 1886 -0859
a) AlCl Py3middot
b) AlCl pyz3middot
c) AlCl pyz AlCl3 3middot middot
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X Y Z
N -4969 0006 -0030
C -4247 0810 0750
C -2861 0771 0775
N -2181 -0091 0006
C -2896 -0902 -0781
C -4285 -0844 -0791
H -4786 1510 1378
H -2284 1423 1416
H -2345 -1599 -1396
H -4854 -1507 -1432
Al 0000 0000 0006
Cl 0000 0000 2193
Cl 0164 -1897 -1071
Cl -0164 1897 -1071
N 2181 0091 0007
C 2896 0902 -0781
C 4285 0844 -0791
N 4969 -0006 -0030
C 4247 -0810 0750C 2861 -0771 0775
H 2345 1599 -1396
H 4854 1507 -1432
H 4786 -1511 1378
H 2284 -1423 1416
d) AlCl (pyz)3 2
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S12
X Y Z
N 0000 -1390 0313
C 0000 -0695 1451
C 0000 0695 1451
N 0000 1390 0313
C 0000 0691 -0830
C 0000 -0691 -0830
H 0000 -1258 2374
H 0000 1258 2374
H 0000 1249 -1755
H 0000 -1249 -1755
Al 0000 3614 0169
Cl 1880 3466 -0928
Cl -1880 3466 -0928
Cl 0000 3798 2342
Al 0000 -3614 0169
Cl -1880 -3466 -0928
Cl 1880 -3466 -0928
Cl 0000 -3798 2342
N 0000 -5757 -0124C 0000 -6214 -1385
C 0000 -7574 -1652N 0000 -8490 -0683
C 0000 -8029 0564C 0000 -6669 0855
H 0000 -5480 -2178H 0000 -7932 -2675
H 0000 -8758 1365
H 0000 -6298 1870N 0000 5757 -0124
C 0000 6669 0855C 0000 8029 0564
N 0000 8490 -0683C 0000 7574 -1652
C 0000 6214 -1385H 0000 6298 1870
H 0000 8758 1365H 0000 7932 -2675
H 0000 5480 -2178
e) (AlCl ) (pyz)3 2 3
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S13
X Y Z
N -1379 0020 -0102
C -0677 1160 -0103
C 0709 1140 -0105
N 1379 -0020 -0102
C 0677 -1160 -0103
C -0709 -1140 -0105
H -1235 2087 -0110
H 1287 2053 -0119
H 1235 -2087 -0110
H -1287 -2053 -0119
Al 3450 0002 -0008
Br 3740 0589 2188
Br 4004 -2153 -0570
Br 3945 1626 -1551
Al -3450 -0002 -0008
Br -3945 -1626 -1551
Br -3740 -0589 2188
Br -4004 2154 -0570
X Y Z
C -4242 0080 -0114
C -3526 1271 -0114
C -2143 1223 -0113
N -1471 0057 -0111
C -2164 -1098 -0113
C -3546 -1123 -0113
H -4026 2230 -0117
H -1539 2120 -0119
H -1577 -2007 -0122
H -4062 -2074 -0116
H -5325 0089 -0116
Al 0541 -0001 0004
Br 0905 -0462 2232
Br 1115 -1718 -1426
Br 1224 2097 -0672
f) AlBr Py3middot
g) AlBr pyz3middot
h) AlBr pyz AlBr3 3middot middot
X Y Z
N 4244 0081 -0125
C 3556 -1060 -0119
C 2169 -1090 -0114
N 1466 0054 -0112
C 2146 1211 -0119
C 3534 1208 -0125
H 4123 -1983 -0121
H 1610 -2016 -0119
H 1565 2123 -0126
H 4082 2142 -0132
Al -0567 -0003 0007
Br -0887 -0431 2243
Br -1216 2091 -0699
Br -1109 -1740 -1402
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S14
X Y Z
N -4996 -0097 0013
C -4277 0761 0737
C -2890 0750 0739
N -2204 -0137 0005
C -2917 -1000 -0728
C -4307 -0970 -0716
H -4819 1482 1338
H -2320 1449 1334
H -2364 -1716 -1319
H -4872 -1676 -1314
Al 0000 0000 -0012
Br 0000 0000 2348
Br 0243 -2033 -1182
Br -0243 2033 -1182
N 2204 0137 0005
C 2917 1000 -0728
C 4307 0970 -0716
N 4996 0097 0013
C 4277 -0761 0737C 2890 -0750 0739
H 2364 1716 -1319H 4872 1676 -1314
H 4819 -1482 1338H 2320 -1449 1334
i) AlBr (pyz)3 2
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S15
X Y Z
N -1391 0048 -0040
C -0646 0600 -1003
C 0739 0552 -0962
N 1391 -0048 0040
C 0646 -0600 1003
C -0739 -0552 0962
H -1169 1088 -1813
H 1332 0999 -1747
H 1169 -1087 1813
H -1332 -0999 1747
Al 3649 0031 0042
Br 3785 -1446 1868
Br 3615 -0823 -2153
Br 3424 2342 0420
Al -3649 -0031 -0042
Br -3424 -2342 -0421
Br -3615 0822 2153
Br -3785 1446 -1867
N -5829 -0094 0032
C -6572 -1191 -0152
C -7961 -1130 -0096
N -8617 0003 0138
C -7867 1090 0320
C -6482 1054 0269
H -6046 -2115 -0341
H -8551 -2026 -0247
H -8382 2024 0513
H -5887 1943 0421
N 5829 0094 -0032
C 6572 1191 0151
C 7961 1130 0096
N 8617 -0003 -0138
C 7867 -1091 -0320
C 6482 -1054 -0269
H 6046 2115 0341
H 8552 2026 0247
H 8382 -2024 -0513
H 5887 -1943 -0420
j) (AlBr ) (pyz)3 2 3
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S16
X Y Z
N 1382 -0013 -0121
C 0682 -1156 -0119
C -0703 -1142 -0120
N -1382 0013 -0121
C -0682 1156 -0119
C 0703 1142 -0120
H 1241 -2082 -0128
H -1277 -2059 -0134
H -1241 2082 -0128
H 1277 2059 -0134
Al -3470 -0006 -0020
I -3767 -0416 2451
I -4124 2286 -0857
I -4054 -1937 -1541
Al 3470 0006 -0020
I 4054 1937 -1541
I 3767 0416 2451
I 4124 -2286 -0857
X Y Z
N -1808 -0040 0000
Al 0220 0038 0000
I 0828 -1193 2134
I 0828 2503 0000
I 0828 -1193 -2134
C -4570 -0274 0000
C -2392 -1255 0000
C -2585 1057 0000
C -3967 0977 0000
C -3765 -1408 0000
H -1727 -2108 0000
H -2066 2007 0000
H -4553 1886 0000
H -4189 -2403 0000
H -5649 -0366 0000
X Y Z
N -4439 0000 -1124
C -3756 1133 -0975
C -2400 1149 -0679
N -1722 0000 -0532
C -2400 -1149 -0679
C -3756 -1133 -0975
H -4299 2063 -1094
H -1843 2070 -0567
H -1843 -2070 -0567
H -4299 -2063 -1094
Al 0249 0000 0041
I 0022 0000 2561
I 1178 -2136 -0957
I 1178 2136 -0957
k) AlI Py3middot
l) AlI pyz3middot
m) AlI pyz AlI3 3middot middot
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S17
X Y Z
N -5010 0212 -0396
C -4286 -0860 -0720
C -2910 -0902 -0560
N -2236 0146 -0063
C -2954 1226 0263
C -4335 1248 0092
H -4816 -1716 -1121
H -2338 -1779 -0827
H -2416 2073 0664
H -4902 2132 0361
Al 0000 0000 0059
I 0000 0000 -2545
I 0252 2176 1448
I -0252 -2176 1448
N 2236 -0146 -0063
C 2954 -1226 0263
C 4335 -1248 0092
N 5010 -0212 -0396
C 4286 0860 -0720
C 2910 0902 -0560
H 2416 -2073 0664
H 4902 -2132 0361
H 4816 1716 -1121
H 2338 1779 -0827
n) AlI (pyz)3 2
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S18
o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
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S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S20
d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
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f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
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i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
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j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
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X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
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n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
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3
Figure S3 Molecular structure of complex (AlBr3middotpyz)infin (3) in the crystal Selected interatomic
distances (Aring) Al3-N1 2133(2) Al3-Br1 23099(15) Al3-Br2 23257(8) Selected bond angles
(deg) Br1-Al3-Br2 11595(3) Br1-Al3-N1 9342(8) Br2-Al3-N1 8638(7) Br2- Al3- Br2rsquo
12809(6) Br2-Al3-N1 9063(7) N1-Al3-N1 17316(13)
Figure S4 Molecular structure of complex (GaCl3middotpyz)infin (4) in the crystal Selected interatomic
distances (Aring) Ga1-N1 2203(5) Ga1-Cl1 21855(14) Ga1-Cl2 2174(2) Selected bond angles
(deg) Cl1-Ga1-Cl2 11732(4) Cl1-Ga1-N1 9050(12) Cl1-Ga1-Cl1 12536(6) Cl1- Ga1-N1
8751(12) Cl2-Ga1-N1 9216(12) N1-Ga1-N1 17568(17)
Figure S5 Molecular structure of complex GaI3middotpyz (5) in the crystal Selected interatomic
distances (Aring) Ga1-N1 2037(6) Ga1-I1 25137(10) Ga1-I2 25094(9) Ga1-I3 25081(11)
Selected bond angles (deg) I1-Ga1-I2 11657(4) I1-Ga1-I3 11209(4) I1-Ga1-N1 10254(16)
I2-Ga1-I3 11383(3) I2-Ga1-N1 10509(16) I3-Ga1-N1 10505(17)
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Table S1 Crystal Structure Information for investigated complexes
empiric formula C4H4Al2Br6N2 (1) C4H4Cl6Ga2N2 (2) C4H4AlBr3N2 (3) C4H4Cl3GaN2 (4) C4H4I3GaN2 (5)
Al2Br6pyz Ga2Cl6pyz (AlBr3pyz)infin (GaCl3pyz)infin GaI3pyz
Mr 61345 43223 34677 25616 53051
crystal size [mm] 032 times 013 times 006 049 times 032 times 023 060 times 025 times 018 013 times 002 times 002 043 times 020 times 020
T [K] 123(1) 123(1) 123(1) 123(1) 123(1)
[Aring] 154178 (Cu) 154178 (Cu) 071073 (Mo) 154178 (Cu) 071073 (Mo)
absorption correction type semi-empirical analytical analytical semi-empirical analytical
space group P21c P21c C2c C2c P
crystal system monoclinic monoclinic monoclinic monoclinic triclinic
a [Aring] 69688(3) 66265(7) 112325(11) 111474(7) 71493(10)
b [Aring] 158935(4) 154544(10) 67023(4) 63189(5) 93992(17)
c [Aring] 75060(3) 71401(8) 118372(19) 115922(8) 95165(12)
[deg] 90 90 90 90 60776(16)
[deg] 117596(5) 115721(13) 104753(14) 101953(7) 79488(12)
[deg] 90 90 90 90 87758(13)
V [Aring3] 73678(6) 65876(13) 86177(18) 79884(10) 54779(17)
Z 2 2 4 4 2
calcd [gcm3] 2765 2179 2673 2130 3216
[mmndash1
] 20616 15948 14072 13328 10908
range [deg] 557 ndash 6506 573 ndash 6668 356 ndash 3051 781 ndash 5892 346 ndash 2650
completeness to 0990 0985 0998 0989 0995
index range ndash7 le h le 6 ndash6 le h le 7 ndash 5 le h le 6 ndash 2 le h le ndash9 le h le 9
ndash 8 le k le 8 ndash 7 le k le 8 ndash7 le k le 9 ndash6le k le6 ndash 2 le k le 12
ndash8 le l le 8 ndash8 le l le 8 ndash 6 le l le 6 ndash 2le l le 2 ndash 2 le l le 2
unique reflections Igt 2 (Rint) 1056 (00713) 1088 (01356) 1027 (00426) 510 (00421) 2125 (0393)
datarestraintsparameters 1250064 1151064 1316048 565047 2573091
GOF in Fsup2 1040 1099 0986 1068 1025
R1wR2(Igt 2 (I)) 0035500841 0093602485 0032200762 0047301127 0040900789
R1wR2 (all data) 0044400877 0095702505 0046100795 0053601149 0055000863
largest diff [e Aring-3
] ndash10140910 ndash25321566 ndash07691265 ndash07721212 ndash14361358
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S5
(a) (b)
(c) (d)
Figure S6 Structures of pyrazine complexes theoretically considered in the present work on the
example of gallium trihalide complexes (a) GaCl3middotpyz (b) (GaCl3)2middotpyz (c) GaCl3middot2pyz (d)
(GaCl3)2middot(pyz)3
N1
Cl3Cl2
Cl1
Cl6Cl5
Ga2N2Ga1
Cl4
N1
Cl3
Cl2
Cl1
Ga1
N1
Cl3
Cl2Cl1
Ga1
N1
Cl3Cl2
Cl1
Cl6
Cl5
Ga2N2
Ga1
Cl4
N3N4
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S6
Table S2 Comparison of theoretically predicted and experimental bond distances (in angstroms)
and bond angles (in degrees)
Compound Method rM-N rM-Х ltN-M-X ltX-M-X
AlCl3∙pyz B3LYP 2028 2134-2138 1019-1028 1151-1162
AlCl3∙pyzAlCl3 B3LYP 2063 21262131 1002-1016 1159-1172
pyz∙AlCl3∙pyz B3LYP 2182 2187 878-922 1195-1210
pyz∙AlCl3∙pyz∙AlCl3∙pyz B3LYP 21632228 2181-2182 880-929 1190-1204
AlBr3∙pyz B3LYP 2037 2299-2303 1016-1038 1150-1156
AlBr3∙pyzAlBr3 B3LYP 2074 2292-2295 999-1027 1158-1166
AlBr3∙pyzAlBr3 (1) X-ray 1999 2247-2267 10085-10443 1134-1169
pyz∙AlBr3∙pyz B3LYP 2208 2359-2361 874-930 1197-1205
pyz∙AlBr3∙pyz∙AlBr3∙pyz B3LYP 2182 2259 2352-2355 884-896 1198-1203
(AlBr3∙pyz)infin (3) X-ray 2133 2310-2326 864-934 1160-1281
AlI3∙pyz B3LYP 2053 2530-2534 1011-1043 1148-1152
AlI3∙pyzAlI3 B3LYP 2090 2522-2526 996-1035 1157-1162
pyz∙AlI3∙pyz B3LYP 2242 2244 2594-2603 867-940 1150-1226
pyz∙AlI3∙pyz∙AlI3∙pyz B3LYP 2215 2330 2586-2591 864-953 1184-1207
GaCl3∙pyz B3LYP 2096 2180-2184 1016-1018 1155-1171
GaCl3∙pyzGaCl3 B3LYP 2141 2173-2177 1000-1004 1163-1180
GaCl3∙pyzGaCl3 (2) X-ray 2044 2135-2147 1016-1034 1130-1169
pyz∙GaCl3∙pyz B3LYP 2276 2223-2224 881-919 1196-1208
pyz∙GaCl3∙pyz∙GaCl3∙pyz B3LYP 2243 2336 2218-2219 867-934 1192-1203
(GaCl3∙pyz)infin (4) X-ray 2203 2174-2186 875-9216 1173-1254
GaBr3∙pyz B3LYP 2113 2334-2337 1011-1026 1154-1165
GaBr3∙pyzGaBr3 B3LYP 2161 2327-2330 994-1014 1162-1175
pyz∙GaBr3∙pyz B3LYP 2326 2377-2378 877-925 1197-1206
pyz∙GaBr3∙pyz∙GaBr3∙pyz B3LYP 2277 2416 2371-2373 859-942 1193-1204
GaI3pyz B3LYP 2143 2551-2553 1004-1027 1157-1161
GaI3pyz (5) X-ray 2027 2504-2509 1026-1051 1121-1167
GaI3∙pyzGaI3 B3LYP 2193 2542-2547 992-1013 1167
pyz∙GaI3∙pyz B3LYP 2424 2425 2586-2589 876-931 1200
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Table S3 Total energies Eordm0 standard enthalpies Hordm298 (in Hartree) and entropies Sordm298 (in
cal mol-1
K-1
) B3LYPTZVP level of theory
Compound Eordm0 Hordm298 Sordm298
AlCl3∙Py -18717591724 -18716513100 108239
AlCl3∙pyz -18877870231 -18876915220 108056
AlCl3∙pyzAlCl3 -35111580608 -35110489670 148691
AlCl3(pyz)2 -21522048075 -21520251440 136595
(AlCl3)2(pyz)3 -40400023628 -40397248410 209795
AlBr3∙Py -82136228039 -82135155080 115781
AlBr3∙pyz -82296506985 -82295557760 115627
AlBr3∙pyzAlBr3 -161948858137 -161947779010 163708
AlBr3(pyz)2 -84940643503 -84938853240 146622
(AlBr3)2(pyz)3 -167237224514 -167234462290 225077
AlI3∙Py -13844590963 -1384352177 121837
AlI3∙pyz -14004871976 -1400392624 124387
AlI3∙pyzAlI3 -25365599319 -2536452716 175051
AlI3(pyz)2 -16648951507 -1664716600 151946
(AlI3)2(pyz)3 -30653841482 -3065108822 233288
GaCl3∙Py -35541541594 -3554046971 111664
GaCl3∙pyz -3570182340 -3570087489 111512
GaCl3∙pyzGaCl3 -6875949899 -6875842102 156295
GaCl3(pyz)2 -3834596631 -3834417720 141855
(GaCl3)2(pyz)3 -7404787740 -7404511645 217400
GaBr3∙Py -98960303362 -98959236330 119336
GaBr3∙pyz -99120587356 -99119643780 119266
GaBr3∙pyzGaBr3 -195597035548 -195595967440 171477
GaBr3(pyz)2 -101764685552 -101762902200 151269
(GaBr3)2(pyz)3 -200885318973 -200882569600 235047
GaI3Py -30668807732 -3066774365 126040
GaI3pyz -30829096463 -3082815563 126682
GaI3∙pyzGaI3 -59014069503 -5901300666 181996
GaI3(pyz)2 -3347313909 -3347136003 159749
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Table S4 BSSE energies kJ mol-1
B3LYPTZVP level of theory
Compound X=Cl X=Br X=I
AlX3py 74 62 45
AlX3pyz 74 61 38
AlX3∙pyzAlX3 146 123 99
AlX3(pyz)2 113 91 57
(AlX3)2(pyz)3 222 183 135
GaX3py 64 54 39
GaX3pyz 62 52 39
GaX3∙pyzGaX3 119 102 78
GaX3(pyz)2 89 73 52
(GaX3)2(pyz)3 181 151 -
Table S5 Structural and energetic parameters of mixed 21 complexes Standard
dissociation enthalpies ΔdissHordm298 kJ mol-1
and standard dissociation entropies ΔdissSordm298 J mol-1
K-1
B3LYPTZVP level of theory
MX3-pyz-MX3 r(N1-M) r(N2-M) ΔdissHordm298 ΔdissSordm298
AlCl3-pyz-GaCl3 2061 2144 1995 2769
AlCl3-pyz-AlBr3 2062 2075 2130 2821
AlCl3-pyz-GaBr3 2059 2167 1877 2787
GaCl3-pyz-AlBr3 2143 2072 1897 2817
GaCl3-pyz-GaBr3 2138 2164 1643 2778
AlBr3-pyz-GaBr3 2070 2166 1779 2829
Table S6 Summary of the tensimetry experiments performed in the AlBr3-pyz system
Experiment
number
Temperature
range K
Number of
heatingcooling runs
AlBr3pyz
ratio
Chemical composition (mass of
the substance in mg)
Volume
ml
1 291-675 3 11 AlBr3pyz (362) 2740
2 293-649 4 11 AlBr3pyz (455) 3337
3 291-660 3 1303 AlBr3pyz (455) pyz (213) 3060
4 5 21 (AlBr3)2pyz (282) 5550
5 12 2031 AlBr3 (514) pyz (76) 5905
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Table S7 Melting points Energies of the M-N bonds EM-N and melting enthalpies ΔmeltH kJ mol-1
Compound EM-N Tmelt K ΔmeltH
(AlBr3pyz)infin (3) 85 540 643b
(GaCl3pyz)infin (4) 77 461-463 [11]a 470 [12] 127 [12]
b
(GaBr3pyz)infin 64 361-363 [11]a
a synthesis in nonaqueous solutions
b estimated as difference between sublimation and vaporization
enthalpies from tensimetry studies
Figure S7 System for synthesis of complexes 1 2 3 and 4 ndash places for the sealing off А ndash
ampoule with known amount of pyrazine B ndash ampoule with known amount of AlBr3 С ndash
compartment for the introduction of pyz D ndash ampoule for removal of the excess component E ndash
reaction volume F ndash ampoule to remove the synthesized complex G ndash capillary for the mass
spectrometry study
E
Zeolites
To vacuum pump
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S10
Figure S8 Optimized structures and xyz coordinates for considered aluminum compounds
B3LYPTZVP level of theory
X Y Z
N -1377 0012 -0093
C -0683 1157 -0096
C 0702 1145 -0097
N 1377 -0011 -0093
C 0683 -1157 -0096
C -0702 -1145 -0097
H -1248 2080 -0108
H 1279 2060 -0113
H 1248 -2079 -0108
H -1278 -2060 -0112
Al 3437 -0001 0008
Cl 3710 0310 2094
Cl 3911 -1943 -0731
Cl 3895 1657 -1249
Al -3438 0001 0008
Cl -3895 -1654 -1252
Cl -3710 -0314 2093
Cl -3911 1945 -0727
X Y Z
N 3671 0002 -0002
C 2969 -1130 -0018
C 1582 -1142 -0050
N 0895 0011 -0063
C 1589 1159 -0050
C 2977 1138 -0019
H 3524 -2061 -0008
H 1009 -2059 -0075
H 1020 2079 -0074
H 3537 2065 -0009
Al -1131 0001 0002
Cl -1502 -0192 2095
Cl -1643 1895 -0845
Cl -1622 -1719 -1167
X Y Z
C -3663 0001 0000
C -2962 1200 -0018
C -1579 1169 -0053
N -0895 0010 -0067
C -1572 -1153 -0054
C -2954 -1194 -0019
H -3473 2153 -0008
H -0985 2072 -0077
H -0973 -2054 -0080
H -3458 -2150 -0010
H -4746 -0003 0026
Al 1113 0001 0002
Cl 1517 -0174 2095
Cl 1639 -1726 -1149
Cl 1656 1886 -0859
a) AlCl Py3middot
b) AlCl pyz3middot
c) AlCl pyz AlCl3 3middot middot
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X Y Z
N -4969 0006 -0030
C -4247 0810 0750
C -2861 0771 0775
N -2181 -0091 0006
C -2896 -0902 -0781
C -4285 -0844 -0791
H -4786 1510 1378
H -2284 1423 1416
H -2345 -1599 -1396
H -4854 -1507 -1432
Al 0000 0000 0006
Cl 0000 0000 2193
Cl 0164 -1897 -1071
Cl -0164 1897 -1071
N 2181 0091 0007
C 2896 0902 -0781
C 4285 0844 -0791
N 4969 -0006 -0030
C 4247 -0810 0750C 2861 -0771 0775
H 2345 1599 -1396
H 4854 1507 -1432
H 4786 -1511 1378
H 2284 -1423 1416
d) AlCl (pyz)3 2
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X Y Z
N 0000 -1390 0313
C 0000 -0695 1451
C 0000 0695 1451
N 0000 1390 0313
C 0000 0691 -0830
C 0000 -0691 -0830
H 0000 -1258 2374
H 0000 1258 2374
H 0000 1249 -1755
H 0000 -1249 -1755
Al 0000 3614 0169
Cl 1880 3466 -0928
Cl -1880 3466 -0928
Cl 0000 3798 2342
Al 0000 -3614 0169
Cl -1880 -3466 -0928
Cl 1880 -3466 -0928
Cl 0000 -3798 2342
N 0000 -5757 -0124C 0000 -6214 -1385
C 0000 -7574 -1652N 0000 -8490 -0683
C 0000 -8029 0564C 0000 -6669 0855
H 0000 -5480 -2178H 0000 -7932 -2675
H 0000 -8758 1365
H 0000 -6298 1870N 0000 5757 -0124
C 0000 6669 0855C 0000 8029 0564
N 0000 8490 -0683C 0000 7574 -1652
C 0000 6214 -1385H 0000 6298 1870
H 0000 8758 1365H 0000 7932 -2675
H 0000 5480 -2178
e) (AlCl ) (pyz)3 2 3
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X Y Z
N -1379 0020 -0102
C -0677 1160 -0103
C 0709 1140 -0105
N 1379 -0020 -0102
C 0677 -1160 -0103
C -0709 -1140 -0105
H -1235 2087 -0110
H 1287 2053 -0119
H 1235 -2087 -0110
H -1287 -2053 -0119
Al 3450 0002 -0008
Br 3740 0589 2188
Br 4004 -2153 -0570
Br 3945 1626 -1551
Al -3450 -0002 -0008
Br -3945 -1626 -1551
Br -3740 -0589 2188
Br -4004 2154 -0570
X Y Z
C -4242 0080 -0114
C -3526 1271 -0114
C -2143 1223 -0113
N -1471 0057 -0111
C -2164 -1098 -0113
C -3546 -1123 -0113
H -4026 2230 -0117
H -1539 2120 -0119
H -1577 -2007 -0122
H -4062 -2074 -0116
H -5325 0089 -0116
Al 0541 -0001 0004
Br 0905 -0462 2232
Br 1115 -1718 -1426
Br 1224 2097 -0672
f) AlBr Py3middot
g) AlBr pyz3middot
h) AlBr pyz AlBr3 3middot middot
X Y Z
N 4244 0081 -0125
C 3556 -1060 -0119
C 2169 -1090 -0114
N 1466 0054 -0112
C 2146 1211 -0119
C 3534 1208 -0125
H 4123 -1983 -0121
H 1610 -2016 -0119
H 1565 2123 -0126
H 4082 2142 -0132
Al -0567 -0003 0007
Br -0887 -0431 2243
Br -1216 2091 -0699
Br -1109 -1740 -1402
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X Y Z
N -4996 -0097 0013
C -4277 0761 0737
C -2890 0750 0739
N -2204 -0137 0005
C -2917 -1000 -0728
C -4307 -0970 -0716
H -4819 1482 1338
H -2320 1449 1334
H -2364 -1716 -1319
H -4872 -1676 -1314
Al 0000 0000 -0012
Br 0000 0000 2348
Br 0243 -2033 -1182
Br -0243 2033 -1182
N 2204 0137 0005
C 2917 1000 -0728
C 4307 0970 -0716
N 4996 0097 0013
C 4277 -0761 0737C 2890 -0750 0739
H 2364 1716 -1319H 4872 1676 -1314
H 4819 -1482 1338H 2320 -1449 1334
i) AlBr (pyz)3 2
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X Y Z
N -1391 0048 -0040
C -0646 0600 -1003
C 0739 0552 -0962
N 1391 -0048 0040
C 0646 -0600 1003
C -0739 -0552 0962
H -1169 1088 -1813
H 1332 0999 -1747
H 1169 -1087 1813
H -1332 -0999 1747
Al 3649 0031 0042
Br 3785 -1446 1868
Br 3615 -0823 -2153
Br 3424 2342 0420
Al -3649 -0031 -0042
Br -3424 -2342 -0421
Br -3615 0822 2153
Br -3785 1446 -1867
N -5829 -0094 0032
C -6572 -1191 -0152
C -7961 -1130 -0096
N -8617 0003 0138
C -7867 1090 0320
C -6482 1054 0269
H -6046 -2115 -0341
H -8551 -2026 -0247
H -8382 2024 0513
H -5887 1943 0421
N 5829 0094 -0032
C 6572 1191 0151
C 7961 1130 0096
N 8617 -0003 -0138
C 7867 -1091 -0320
C 6482 -1054 -0269
H 6046 2115 0341
H 8552 2026 0247
H 8382 -2024 -0513
H 5887 -1943 -0420
j) (AlBr ) (pyz)3 2 3
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X Y Z
N 1382 -0013 -0121
C 0682 -1156 -0119
C -0703 -1142 -0120
N -1382 0013 -0121
C -0682 1156 -0119
C 0703 1142 -0120
H 1241 -2082 -0128
H -1277 -2059 -0134
H -1241 2082 -0128
H 1277 2059 -0134
Al -3470 -0006 -0020
I -3767 -0416 2451
I -4124 2286 -0857
I -4054 -1937 -1541
Al 3470 0006 -0020
I 4054 1937 -1541
I 3767 0416 2451
I 4124 -2286 -0857
X Y Z
N -1808 -0040 0000
Al 0220 0038 0000
I 0828 -1193 2134
I 0828 2503 0000
I 0828 -1193 -2134
C -4570 -0274 0000
C -2392 -1255 0000
C -2585 1057 0000
C -3967 0977 0000
C -3765 -1408 0000
H -1727 -2108 0000
H -2066 2007 0000
H -4553 1886 0000
H -4189 -2403 0000
H -5649 -0366 0000
X Y Z
N -4439 0000 -1124
C -3756 1133 -0975
C -2400 1149 -0679
N -1722 0000 -0532
C -2400 -1149 -0679
C -3756 -1133 -0975
H -4299 2063 -1094
H -1843 2070 -0567
H -1843 -2070 -0567
H -4299 -2063 -1094
Al 0249 0000 0041
I 0022 0000 2561
I 1178 -2136 -0957
I 1178 2136 -0957
k) AlI Py3middot
l) AlI pyz3middot
m) AlI pyz AlI3 3middot middot
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X Y Z
N -5010 0212 -0396
C -4286 -0860 -0720
C -2910 -0902 -0560
N -2236 0146 -0063
C -2954 1226 0263
C -4335 1248 0092
H -4816 -1716 -1121
H -2338 -1779 -0827
H -2416 2073 0664
H -4902 2132 0361
Al 0000 0000 0059
I 0000 0000 -2545
I 0252 2176 1448
I -0252 -2176 1448
N 2236 -0146 -0063
C 2954 -1226 0263
C 4335 -1248 0092
N 5010 -0212 -0396
C 4286 0860 -0720
C 2910 0902 -0560
H 2416 -2073 0664
H 4902 -2132 0361
H 4816 1716 -1121
H 2338 1779 -0827
n) AlI (pyz)3 2
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o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
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S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
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d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
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e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
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f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
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i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
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j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
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X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
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n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
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4
Table S1 Crystal Structure Information for investigated complexes
empiric formula C4H4Al2Br6N2 (1) C4H4Cl6Ga2N2 (2) C4H4AlBr3N2 (3) C4H4Cl3GaN2 (4) C4H4I3GaN2 (5)
Al2Br6pyz Ga2Cl6pyz (AlBr3pyz)infin (GaCl3pyz)infin GaI3pyz
Mr 61345 43223 34677 25616 53051
crystal size [mm] 032 times 013 times 006 049 times 032 times 023 060 times 025 times 018 013 times 002 times 002 043 times 020 times 020
T [K] 123(1) 123(1) 123(1) 123(1) 123(1)
[Aring] 154178 (Cu) 154178 (Cu) 071073 (Mo) 154178 (Cu) 071073 (Mo)
absorption correction type semi-empirical analytical analytical semi-empirical analytical
space group P21c P21c C2c C2c P
crystal system monoclinic monoclinic monoclinic monoclinic triclinic
a [Aring] 69688(3) 66265(7) 112325(11) 111474(7) 71493(10)
b [Aring] 158935(4) 154544(10) 67023(4) 63189(5) 93992(17)
c [Aring] 75060(3) 71401(8) 118372(19) 115922(8) 95165(12)
[deg] 90 90 90 90 60776(16)
[deg] 117596(5) 115721(13) 104753(14) 101953(7) 79488(12)
[deg] 90 90 90 90 87758(13)
V [Aring3] 73678(6) 65876(13) 86177(18) 79884(10) 54779(17)
Z 2 2 4 4 2
calcd [gcm3] 2765 2179 2673 2130 3216
[mmndash1
] 20616 15948 14072 13328 10908
range [deg] 557 ndash 6506 573 ndash 6668 356 ndash 3051 781 ndash 5892 346 ndash 2650
completeness to 0990 0985 0998 0989 0995
index range ndash7 le h le 6 ndash6 le h le 7 ndash 5 le h le 6 ndash 2 le h le ndash9 le h le 9
ndash 8 le k le 8 ndash 7 le k le 8 ndash7 le k le 9 ndash6le k le6 ndash 2 le k le 12
ndash8 le l le 8 ndash8 le l le 8 ndash 6 le l le 6 ndash 2le l le 2 ndash 2 le l le 2
unique reflections Igt 2 (Rint) 1056 (00713) 1088 (01356) 1027 (00426) 510 (00421) 2125 (0393)
datarestraintsparameters 1250064 1151064 1316048 565047 2573091
GOF in Fsup2 1040 1099 0986 1068 1025
R1wR2(Igt 2 (I)) 0035500841 0093602485 0032200762 0047301127 0040900789
R1wR2 (all data) 0044400877 0095702505 0046100795 0053601149 0055000863
largest diff [e Aring-3
] ndash10140910 ndash25321566 ndash07691265 ndash07721212 ndash14361358
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(a) (b)
(c) (d)
Figure S6 Structures of pyrazine complexes theoretically considered in the present work on the
example of gallium trihalide complexes (a) GaCl3middotpyz (b) (GaCl3)2middotpyz (c) GaCl3middot2pyz (d)
(GaCl3)2middot(pyz)3
N1
Cl3Cl2
Cl1
Cl6Cl5
Ga2N2Ga1
Cl4
N1
Cl3
Cl2
Cl1
Ga1
N1
Cl3
Cl2Cl1
Ga1
N1
Cl3Cl2
Cl1
Cl6
Cl5
Ga2N2
Ga1
Cl4
N3N4
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Table S2 Comparison of theoretically predicted and experimental bond distances (in angstroms)
and bond angles (in degrees)
Compound Method rM-N rM-Х ltN-M-X ltX-M-X
AlCl3∙pyz B3LYP 2028 2134-2138 1019-1028 1151-1162
AlCl3∙pyzAlCl3 B3LYP 2063 21262131 1002-1016 1159-1172
pyz∙AlCl3∙pyz B3LYP 2182 2187 878-922 1195-1210
pyz∙AlCl3∙pyz∙AlCl3∙pyz B3LYP 21632228 2181-2182 880-929 1190-1204
AlBr3∙pyz B3LYP 2037 2299-2303 1016-1038 1150-1156
AlBr3∙pyzAlBr3 B3LYP 2074 2292-2295 999-1027 1158-1166
AlBr3∙pyzAlBr3 (1) X-ray 1999 2247-2267 10085-10443 1134-1169
pyz∙AlBr3∙pyz B3LYP 2208 2359-2361 874-930 1197-1205
pyz∙AlBr3∙pyz∙AlBr3∙pyz B3LYP 2182 2259 2352-2355 884-896 1198-1203
(AlBr3∙pyz)infin (3) X-ray 2133 2310-2326 864-934 1160-1281
AlI3∙pyz B3LYP 2053 2530-2534 1011-1043 1148-1152
AlI3∙pyzAlI3 B3LYP 2090 2522-2526 996-1035 1157-1162
pyz∙AlI3∙pyz B3LYP 2242 2244 2594-2603 867-940 1150-1226
pyz∙AlI3∙pyz∙AlI3∙pyz B3LYP 2215 2330 2586-2591 864-953 1184-1207
GaCl3∙pyz B3LYP 2096 2180-2184 1016-1018 1155-1171
GaCl3∙pyzGaCl3 B3LYP 2141 2173-2177 1000-1004 1163-1180
GaCl3∙pyzGaCl3 (2) X-ray 2044 2135-2147 1016-1034 1130-1169
pyz∙GaCl3∙pyz B3LYP 2276 2223-2224 881-919 1196-1208
pyz∙GaCl3∙pyz∙GaCl3∙pyz B3LYP 2243 2336 2218-2219 867-934 1192-1203
(GaCl3∙pyz)infin (4) X-ray 2203 2174-2186 875-9216 1173-1254
GaBr3∙pyz B3LYP 2113 2334-2337 1011-1026 1154-1165
GaBr3∙pyzGaBr3 B3LYP 2161 2327-2330 994-1014 1162-1175
pyz∙GaBr3∙pyz B3LYP 2326 2377-2378 877-925 1197-1206
pyz∙GaBr3∙pyz∙GaBr3∙pyz B3LYP 2277 2416 2371-2373 859-942 1193-1204
GaI3pyz B3LYP 2143 2551-2553 1004-1027 1157-1161
GaI3pyz (5) X-ray 2027 2504-2509 1026-1051 1121-1167
GaI3∙pyzGaI3 B3LYP 2193 2542-2547 992-1013 1167
pyz∙GaI3∙pyz B3LYP 2424 2425 2586-2589 876-931 1200
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Table S3 Total energies Eordm0 standard enthalpies Hordm298 (in Hartree) and entropies Sordm298 (in
cal mol-1
K-1
) B3LYPTZVP level of theory
Compound Eordm0 Hordm298 Sordm298
AlCl3∙Py -18717591724 -18716513100 108239
AlCl3∙pyz -18877870231 -18876915220 108056
AlCl3∙pyzAlCl3 -35111580608 -35110489670 148691
AlCl3(pyz)2 -21522048075 -21520251440 136595
(AlCl3)2(pyz)3 -40400023628 -40397248410 209795
AlBr3∙Py -82136228039 -82135155080 115781
AlBr3∙pyz -82296506985 -82295557760 115627
AlBr3∙pyzAlBr3 -161948858137 -161947779010 163708
AlBr3(pyz)2 -84940643503 -84938853240 146622
(AlBr3)2(pyz)3 -167237224514 -167234462290 225077
AlI3∙Py -13844590963 -1384352177 121837
AlI3∙pyz -14004871976 -1400392624 124387
AlI3∙pyzAlI3 -25365599319 -2536452716 175051
AlI3(pyz)2 -16648951507 -1664716600 151946
(AlI3)2(pyz)3 -30653841482 -3065108822 233288
GaCl3∙Py -35541541594 -3554046971 111664
GaCl3∙pyz -3570182340 -3570087489 111512
GaCl3∙pyzGaCl3 -6875949899 -6875842102 156295
GaCl3(pyz)2 -3834596631 -3834417720 141855
(GaCl3)2(pyz)3 -7404787740 -7404511645 217400
GaBr3∙Py -98960303362 -98959236330 119336
GaBr3∙pyz -99120587356 -99119643780 119266
GaBr3∙pyzGaBr3 -195597035548 -195595967440 171477
GaBr3(pyz)2 -101764685552 -101762902200 151269
(GaBr3)2(pyz)3 -200885318973 -200882569600 235047
GaI3Py -30668807732 -3066774365 126040
GaI3pyz -30829096463 -3082815563 126682
GaI3∙pyzGaI3 -59014069503 -5901300666 181996
GaI3(pyz)2 -3347313909 -3347136003 159749
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Table S4 BSSE energies kJ mol-1
B3LYPTZVP level of theory
Compound X=Cl X=Br X=I
AlX3py 74 62 45
AlX3pyz 74 61 38
AlX3∙pyzAlX3 146 123 99
AlX3(pyz)2 113 91 57
(AlX3)2(pyz)3 222 183 135
GaX3py 64 54 39
GaX3pyz 62 52 39
GaX3∙pyzGaX3 119 102 78
GaX3(pyz)2 89 73 52
(GaX3)2(pyz)3 181 151 -
Table S5 Structural and energetic parameters of mixed 21 complexes Standard
dissociation enthalpies ΔdissHordm298 kJ mol-1
and standard dissociation entropies ΔdissSordm298 J mol-1
K-1
B3LYPTZVP level of theory
MX3-pyz-MX3 r(N1-M) r(N2-M) ΔdissHordm298 ΔdissSordm298
AlCl3-pyz-GaCl3 2061 2144 1995 2769
AlCl3-pyz-AlBr3 2062 2075 2130 2821
AlCl3-pyz-GaBr3 2059 2167 1877 2787
GaCl3-pyz-AlBr3 2143 2072 1897 2817
GaCl3-pyz-GaBr3 2138 2164 1643 2778
AlBr3-pyz-GaBr3 2070 2166 1779 2829
Table S6 Summary of the tensimetry experiments performed in the AlBr3-pyz system
Experiment
number
Temperature
range K
Number of
heatingcooling runs
AlBr3pyz
ratio
Chemical composition (mass of
the substance in mg)
Volume
ml
1 291-675 3 11 AlBr3pyz (362) 2740
2 293-649 4 11 AlBr3pyz (455) 3337
3 291-660 3 1303 AlBr3pyz (455) pyz (213) 3060
4 5 21 (AlBr3)2pyz (282) 5550
5 12 2031 AlBr3 (514) pyz (76) 5905
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Table S7 Melting points Energies of the M-N bonds EM-N and melting enthalpies ΔmeltH kJ mol-1
Compound EM-N Tmelt K ΔmeltH
(AlBr3pyz)infin (3) 85 540 643b
(GaCl3pyz)infin (4) 77 461-463 [11]a 470 [12] 127 [12]
b
(GaBr3pyz)infin 64 361-363 [11]a
a synthesis in nonaqueous solutions
b estimated as difference between sublimation and vaporization
enthalpies from tensimetry studies
Figure S7 System for synthesis of complexes 1 2 3 and 4 ndash places for the sealing off А ndash
ampoule with known amount of pyrazine B ndash ampoule with known amount of AlBr3 С ndash
compartment for the introduction of pyz D ndash ampoule for removal of the excess component E ndash
reaction volume F ndash ampoule to remove the synthesized complex G ndash capillary for the mass
spectrometry study
E
Zeolites
To vacuum pump
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S10
Figure S8 Optimized structures and xyz coordinates for considered aluminum compounds
B3LYPTZVP level of theory
X Y Z
N -1377 0012 -0093
C -0683 1157 -0096
C 0702 1145 -0097
N 1377 -0011 -0093
C 0683 -1157 -0096
C -0702 -1145 -0097
H -1248 2080 -0108
H 1279 2060 -0113
H 1248 -2079 -0108
H -1278 -2060 -0112
Al 3437 -0001 0008
Cl 3710 0310 2094
Cl 3911 -1943 -0731
Cl 3895 1657 -1249
Al -3438 0001 0008
Cl -3895 -1654 -1252
Cl -3710 -0314 2093
Cl -3911 1945 -0727
X Y Z
N 3671 0002 -0002
C 2969 -1130 -0018
C 1582 -1142 -0050
N 0895 0011 -0063
C 1589 1159 -0050
C 2977 1138 -0019
H 3524 -2061 -0008
H 1009 -2059 -0075
H 1020 2079 -0074
H 3537 2065 -0009
Al -1131 0001 0002
Cl -1502 -0192 2095
Cl -1643 1895 -0845
Cl -1622 -1719 -1167
X Y Z
C -3663 0001 0000
C -2962 1200 -0018
C -1579 1169 -0053
N -0895 0010 -0067
C -1572 -1153 -0054
C -2954 -1194 -0019
H -3473 2153 -0008
H -0985 2072 -0077
H -0973 -2054 -0080
H -3458 -2150 -0010
H -4746 -0003 0026
Al 1113 0001 0002
Cl 1517 -0174 2095
Cl 1639 -1726 -1149
Cl 1656 1886 -0859
a) AlCl Py3middot
b) AlCl pyz3middot
c) AlCl pyz AlCl3 3middot middot
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S11
X Y Z
N -4969 0006 -0030
C -4247 0810 0750
C -2861 0771 0775
N -2181 -0091 0006
C -2896 -0902 -0781
C -4285 -0844 -0791
H -4786 1510 1378
H -2284 1423 1416
H -2345 -1599 -1396
H -4854 -1507 -1432
Al 0000 0000 0006
Cl 0000 0000 2193
Cl 0164 -1897 -1071
Cl -0164 1897 -1071
N 2181 0091 0007
C 2896 0902 -0781
C 4285 0844 -0791
N 4969 -0006 -0030
C 4247 -0810 0750C 2861 -0771 0775
H 2345 1599 -1396
H 4854 1507 -1432
H 4786 -1511 1378
H 2284 -1423 1416
d) AlCl (pyz)3 2
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S12
X Y Z
N 0000 -1390 0313
C 0000 -0695 1451
C 0000 0695 1451
N 0000 1390 0313
C 0000 0691 -0830
C 0000 -0691 -0830
H 0000 -1258 2374
H 0000 1258 2374
H 0000 1249 -1755
H 0000 -1249 -1755
Al 0000 3614 0169
Cl 1880 3466 -0928
Cl -1880 3466 -0928
Cl 0000 3798 2342
Al 0000 -3614 0169
Cl -1880 -3466 -0928
Cl 1880 -3466 -0928
Cl 0000 -3798 2342
N 0000 -5757 -0124C 0000 -6214 -1385
C 0000 -7574 -1652N 0000 -8490 -0683
C 0000 -8029 0564C 0000 -6669 0855
H 0000 -5480 -2178H 0000 -7932 -2675
H 0000 -8758 1365
H 0000 -6298 1870N 0000 5757 -0124
C 0000 6669 0855C 0000 8029 0564
N 0000 8490 -0683C 0000 7574 -1652
C 0000 6214 -1385H 0000 6298 1870
H 0000 8758 1365H 0000 7932 -2675
H 0000 5480 -2178
e) (AlCl ) (pyz)3 2 3
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S13
X Y Z
N -1379 0020 -0102
C -0677 1160 -0103
C 0709 1140 -0105
N 1379 -0020 -0102
C 0677 -1160 -0103
C -0709 -1140 -0105
H -1235 2087 -0110
H 1287 2053 -0119
H 1235 -2087 -0110
H -1287 -2053 -0119
Al 3450 0002 -0008
Br 3740 0589 2188
Br 4004 -2153 -0570
Br 3945 1626 -1551
Al -3450 -0002 -0008
Br -3945 -1626 -1551
Br -3740 -0589 2188
Br -4004 2154 -0570
X Y Z
C -4242 0080 -0114
C -3526 1271 -0114
C -2143 1223 -0113
N -1471 0057 -0111
C -2164 -1098 -0113
C -3546 -1123 -0113
H -4026 2230 -0117
H -1539 2120 -0119
H -1577 -2007 -0122
H -4062 -2074 -0116
H -5325 0089 -0116
Al 0541 -0001 0004
Br 0905 -0462 2232
Br 1115 -1718 -1426
Br 1224 2097 -0672
f) AlBr Py3middot
g) AlBr pyz3middot
h) AlBr pyz AlBr3 3middot middot
X Y Z
N 4244 0081 -0125
C 3556 -1060 -0119
C 2169 -1090 -0114
N 1466 0054 -0112
C 2146 1211 -0119
C 3534 1208 -0125
H 4123 -1983 -0121
H 1610 -2016 -0119
H 1565 2123 -0126
H 4082 2142 -0132
Al -0567 -0003 0007
Br -0887 -0431 2243
Br -1216 2091 -0699
Br -1109 -1740 -1402
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S14
X Y Z
N -4996 -0097 0013
C -4277 0761 0737
C -2890 0750 0739
N -2204 -0137 0005
C -2917 -1000 -0728
C -4307 -0970 -0716
H -4819 1482 1338
H -2320 1449 1334
H -2364 -1716 -1319
H -4872 -1676 -1314
Al 0000 0000 -0012
Br 0000 0000 2348
Br 0243 -2033 -1182
Br -0243 2033 -1182
N 2204 0137 0005
C 2917 1000 -0728
C 4307 0970 -0716
N 4996 0097 0013
C 4277 -0761 0737C 2890 -0750 0739
H 2364 1716 -1319H 4872 1676 -1314
H 4819 -1482 1338H 2320 -1449 1334
i) AlBr (pyz)3 2
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S15
X Y Z
N -1391 0048 -0040
C -0646 0600 -1003
C 0739 0552 -0962
N 1391 -0048 0040
C 0646 -0600 1003
C -0739 -0552 0962
H -1169 1088 -1813
H 1332 0999 -1747
H 1169 -1087 1813
H -1332 -0999 1747
Al 3649 0031 0042
Br 3785 -1446 1868
Br 3615 -0823 -2153
Br 3424 2342 0420
Al -3649 -0031 -0042
Br -3424 -2342 -0421
Br -3615 0822 2153
Br -3785 1446 -1867
N -5829 -0094 0032
C -6572 -1191 -0152
C -7961 -1130 -0096
N -8617 0003 0138
C -7867 1090 0320
C -6482 1054 0269
H -6046 -2115 -0341
H -8551 -2026 -0247
H -8382 2024 0513
H -5887 1943 0421
N 5829 0094 -0032
C 6572 1191 0151
C 7961 1130 0096
N 8617 -0003 -0138
C 7867 -1091 -0320
C 6482 -1054 -0269
H 6046 2115 0341
H 8552 2026 0247
H 8382 -2024 -0513
H 5887 -1943 -0420
j) (AlBr ) (pyz)3 2 3
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S16
X Y Z
N 1382 -0013 -0121
C 0682 -1156 -0119
C -0703 -1142 -0120
N -1382 0013 -0121
C -0682 1156 -0119
C 0703 1142 -0120
H 1241 -2082 -0128
H -1277 -2059 -0134
H -1241 2082 -0128
H 1277 2059 -0134
Al -3470 -0006 -0020
I -3767 -0416 2451
I -4124 2286 -0857
I -4054 -1937 -1541
Al 3470 0006 -0020
I 4054 1937 -1541
I 3767 0416 2451
I 4124 -2286 -0857
X Y Z
N -1808 -0040 0000
Al 0220 0038 0000
I 0828 -1193 2134
I 0828 2503 0000
I 0828 -1193 -2134
C -4570 -0274 0000
C -2392 -1255 0000
C -2585 1057 0000
C -3967 0977 0000
C -3765 -1408 0000
H -1727 -2108 0000
H -2066 2007 0000
H -4553 1886 0000
H -4189 -2403 0000
H -5649 -0366 0000
X Y Z
N -4439 0000 -1124
C -3756 1133 -0975
C -2400 1149 -0679
N -1722 0000 -0532
C -2400 -1149 -0679
C -3756 -1133 -0975
H -4299 2063 -1094
H -1843 2070 -0567
H -1843 -2070 -0567
H -4299 -2063 -1094
Al 0249 0000 0041
I 0022 0000 2561
I 1178 -2136 -0957
I 1178 2136 -0957
k) AlI Py3middot
l) AlI pyz3middot
m) AlI pyz AlI3 3middot middot
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S17
X Y Z
N -5010 0212 -0396
C -4286 -0860 -0720
C -2910 -0902 -0560
N -2236 0146 -0063
C -2954 1226 0263
C -4335 1248 0092
H -4816 -1716 -1121
H -2338 -1779 -0827
H -2416 2073 0664
H -4902 2132 0361
Al 0000 0000 0059
I 0000 0000 -2545
I 0252 2176 1448
I -0252 -2176 1448
N 2236 -0146 -0063
C 2954 -1226 0263
C 4335 -1248 0092
N 5010 -0212 -0396
C 4286 0860 -0720
C 2910 0902 -0560
H 2416 -2073 0664
H 4902 -2132 0361
H 4816 1716 -1121
H 2338 1779 -0827
n) AlI (pyz)3 2
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S18
o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
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S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
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S20
d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
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S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
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f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
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S23
i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
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j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
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S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
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S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
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S5
(a) (b)
(c) (d)
Figure S6 Structures of pyrazine complexes theoretically considered in the present work on the
example of gallium trihalide complexes (a) GaCl3middotpyz (b) (GaCl3)2middotpyz (c) GaCl3middot2pyz (d)
(GaCl3)2middot(pyz)3
N1
Cl3Cl2
Cl1
Cl6Cl5
Ga2N2Ga1
Cl4
N1
Cl3
Cl2
Cl1
Ga1
N1
Cl3
Cl2Cl1
Ga1
N1
Cl3Cl2
Cl1
Cl6
Cl5
Ga2N2
Ga1
Cl4
N3N4
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S6
Table S2 Comparison of theoretically predicted and experimental bond distances (in angstroms)
and bond angles (in degrees)
Compound Method rM-N rM-Х ltN-M-X ltX-M-X
AlCl3∙pyz B3LYP 2028 2134-2138 1019-1028 1151-1162
AlCl3∙pyzAlCl3 B3LYP 2063 21262131 1002-1016 1159-1172
pyz∙AlCl3∙pyz B3LYP 2182 2187 878-922 1195-1210
pyz∙AlCl3∙pyz∙AlCl3∙pyz B3LYP 21632228 2181-2182 880-929 1190-1204
AlBr3∙pyz B3LYP 2037 2299-2303 1016-1038 1150-1156
AlBr3∙pyzAlBr3 B3LYP 2074 2292-2295 999-1027 1158-1166
AlBr3∙pyzAlBr3 (1) X-ray 1999 2247-2267 10085-10443 1134-1169
pyz∙AlBr3∙pyz B3LYP 2208 2359-2361 874-930 1197-1205
pyz∙AlBr3∙pyz∙AlBr3∙pyz B3LYP 2182 2259 2352-2355 884-896 1198-1203
(AlBr3∙pyz)infin (3) X-ray 2133 2310-2326 864-934 1160-1281
AlI3∙pyz B3LYP 2053 2530-2534 1011-1043 1148-1152
AlI3∙pyzAlI3 B3LYP 2090 2522-2526 996-1035 1157-1162
pyz∙AlI3∙pyz B3LYP 2242 2244 2594-2603 867-940 1150-1226
pyz∙AlI3∙pyz∙AlI3∙pyz B3LYP 2215 2330 2586-2591 864-953 1184-1207
GaCl3∙pyz B3LYP 2096 2180-2184 1016-1018 1155-1171
GaCl3∙pyzGaCl3 B3LYP 2141 2173-2177 1000-1004 1163-1180
GaCl3∙pyzGaCl3 (2) X-ray 2044 2135-2147 1016-1034 1130-1169
pyz∙GaCl3∙pyz B3LYP 2276 2223-2224 881-919 1196-1208
pyz∙GaCl3∙pyz∙GaCl3∙pyz B3LYP 2243 2336 2218-2219 867-934 1192-1203
(GaCl3∙pyz)infin (4) X-ray 2203 2174-2186 875-9216 1173-1254
GaBr3∙pyz B3LYP 2113 2334-2337 1011-1026 1154-1165
GaBr3∙pyzGaBr3 B3LYP 2161 2327-2330 994-1014 1162-1175
pyz∙GaBr3∙pyz B3LYP 2326 2377-2378 877-925 1197-1206
pyz∙GaBr3∙pyz∙GaBr3∙pyz B3LYP 2277 2416 2371-2373 859-942 1193-1204
GaI3pyz B3LYP 2143 2551-2553 1004-1027 1157-1161
GaI3pyz (5) X-ray 2027 2504-2509 1026-1051 1121-1167
GaI3∙pyzGaI3 B3LYP 2193 2542-2547 992-1013 1167
pyz∙GaI3∙pyz B3LYP 2424 2425 2586-2589 876-931 1200
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S7
Table S3 Total energies Eordm0 standard enthalpies Hordm298 (in Hartree) and entropies Sordm298 (in
cal mol-1
K-1
) B3LYPTZVP level of theory
Compound Eordm0 Hordm298 Sordm298
AlCl3∙Py -18717591724 -18716513100 108239
AlCl3∙pyz -18877870231 -18876915220 108056
AlCl3∙pyzAlCl3 -35111580608 -35110489670 148691
AlCl3(pyz)2 -21522048075 -21520251440 136595
(AlCl3)2(pyz)3 -40400023628 -40397248410 209795
AlBr3∙Py -82136228039 -82135155080 115781
AlBr3∙pyz -82296506985 -82295557760 115627
AlBr3∙pyzAlBr3 -161948858137 -161947779010 163708
AlBr3(pyz)2 -84940643503 -84938853240 146622
(AlBr3)2(pyz)3 -167237224514 -167234462290 225077
AlI3∙Py -13844590963 -1384352177 121837
AlI3∙pyz -14004871976 -1400392624 124387
AlI3∙pyzAlI3 -25365599319 -2536452716 175051
AlI3(pyz)2 -16648951507 -1664716600 151946
(AlI3)2(pyz)3 -30653841482 -3065108822 233288
GaCl3∙Py -35541541594 -3554046971 111664
GaCl3∙pyz -3570182340 -3570087489 111512
GaCl3∙pyzGaCl3 -6875949899 -6875842102 156295
GaCl3(pyz)2 -3834596631 -3834417720 141855
(GaCl3)2(pyz)3 -7404787740 -7404511645 217400
GaBr3∙Py -98960303362 -98959236330 119336
GaBr3∙pyz -99120587356 -99119643780 119266
GaBr3∙pyzGaBr3 -195597035548 -195595967440 171477
GaBr3(pyz)2 -101764685552 -101762902200 151269
(GaBr3)2(pyz)3 -200885318973 -200882569600 235047
GaI3Py -30668807732 -3066774365 126040
GaI3pyz -30829096463 -3082815563 126682
GaI3∙pyzGaI3 -59014069503 -5901300666 181996
GaI3(pyz)2 -3347313909 -3347136003 159749
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S8
Table S4 BSSE energies kJ mol-1
B3LYPTZVP level of theory
Compound X=Cl X=Br X=I
AlX3py 74 62 45
AlX3pyz 74 61 38
AlX3∙pyzAlX3 146 123 99
AlX3(pyz)2 113 91 57
(AlX3)2(pyz)3 222 183 135
GaX3py 64 54 39
GaX3pyz 62 52 39
GaX3∙pyzGaX3 119 102 78
GaX3(pyz)2 89 73 52
(GaX3)2(pyz)3 181 151 -
Table S5 Structural and energetic parameters of mixed 21 complexes Standard
dissociation enthalpies ΔdissHordm298 kJ mol-1
and standard dissociation entropies ΔdissSordm298 J mol-1
K-1
B3LYPTZVP level of theory
MX3-pyz-MX3 r(N1-M) r(N2-M) ΔdissHordm298 ΔdissSordm298
AlCl3-pyz-GaCl3 2061 2144 1995 2769
AlCl3-pyz-AlBr3 2062 2075 2130 2821
AlCl3-pyz-GaBr3 2059 2167 1877 2787
GaCl3-pyz-AlBr3 2143 2072 1897 2817
GaCl3-pyz-GaBr3 2138 2164 1643 2778
AlBr3-pyz-GaBr3 2070 2166 1779 2829
Table S6 Summary of the tensimetry experiments performed in the AlBr3-pyz system
Experiment
number
Temperature
range K
Number of
heatingcooling runs
AlBr3pyz
ratio
Chemical composition (mass of
the substance in mg)
Volume
ml
1 291-675 3 11 AlBr3pyz (362) 2740
2 293-649 4 11 AlBr3pyz (455) 3337
3 291-660 3 1303 AlBr3pyz (455) pyz (213) 3060
4 5 21 (AlBr3)2pyz (282) 5550
5 12 2031 AlBr3 (514) pyz (76) 5905
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S9
Table S7 Melting points Energies of the M-N bonds EM-N and melting enthalpies ΔmeltH kJ mol-1
Compound EM-N Tmelt K ΔmeltH
(AlBr3pyz)infin (3) 85 540 643b
(GaCl3pyz)infin (4) 77 461-463 [11]a 470 [12] 127 [12]
b
(GaBr3pyz)infin 64 361-363 [11]a
a synthesis in nonaqueous solutions
b estimated as difference between sublimation and vaporization
enthalpies from tensimetry studies
Figure S7 System for synthesis of complexes 1 2 3 and 4 ndash places for the sealing off А ndash
ampoule with known amount of pyrazine B ndash ampoule with known amount of AlBr3 С ndash
compartment for the introduction of pyz D ndash ampoule for removal of the excess component E ndash
reaction volume F ndash ampoule to remove the synthesized complex G ndash capillary for the mass
spectrometry study
E
Zeolites
To vacuum pump
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S10
Figure S8 Optimized structures and xyz coordinates for considered aluminum compounds
B3LYPTZVP level of theory
X Y Z
N -1377 0012 -0093
C -0683 1157 -0096
C 0702 1145 -0097
N 1377 -0011 -0093
C 0683 -1157 -0096
C -0702 -1145 -0097
H -1248 2080 -0108
H 1279 2060 -0113
H 1248 -2079 -0108
H -1278 -2060 -0112
Al 3437 -0001 0008
Cl 3710 0310 2094
Cl 3911 -1943 -0731
Cl 3895 1657 -1249
Al -3438 0001 0008
Cl -3895 -1654 -1252
Cl -3710 -0314 2093
Cl -3911 1945 -0727
X Y Z
N 3671 0002 -0002
C 2969 -1130 -0018
C 1582 -1142 -0050
N 0895 0011 -0063
C 1589 1159 -0050
C 2977 1138 -0019
H 3524 -2061 -0008
H 1009 -2059 -0075
H 1020 2079 -0074
H 3537 2065 -0009
Al -1131 0001 0002
Cl -1502 -0192 2095
Cl -1643 1895 -0845
Cl -1622 -1719 -1167
X Y Z
C -3663 0001 0000
C -2962 1200 -0018
C -1579 1169 -0053
N -0895 0010 -0067
C -1572 -1153 -0054
C -2954 -1194 -0019
H -3473 2153 -0008
H -0985 2072 -0077
H -0973 -2054 -0080
H -3458 -2150 -0010
H -4746 -0003 0026
Al 1113 0001 0002
Cl 1517 -0174 2095
Cl 1639 -1726 -1149
Cl 1656 1886 -0859
a) AlCl Py3middot
b) AlCl pyz3middot
c) AlCl pyz AlCl3 3middot middot
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X Y Z
N -4969 0006 -0030
C -4247 0810 0750
C -2861 0771 0775
N -2181 -0091 0006
C -2896 -0902 -0781
C -4285 -0844 -0791
H -4786 1510 1378
H -2284 1423 1416
H -2345 -1599 -1396
H -4854 -1507 -1432
Al 0000 0000 0006
Cl 0000 0000 2193
Cl 0164 -1897 -1071
Cl -0164 1897 -1071
N 2181 0091 0007
C 2896 0902 -0781
C 4285 0844 -0791
N 4969 -0006 -0030
C 4247 -0810 0750C 2861 -0771 0775
H 2345 1599 -1396
H 4854 1507 -1432
H 4786 -1511 1378
H 2284 -1423 1416
d) AlCl (pyz)3 2
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X Y Z
N 0000 -1390 0313
C 0000 -0695 1451
C 0000 0695 1451
N 0000 1390 0313
C 0000 0691 -0830
C 0000 -0691 -0830
H 0000 -1258 2374
H 0000 1258 2374
H 0000 1249 -1755
H 0000 -1249 -1755
Al 0000 3614 0169
Cl 1880 3466 -0928
Cl -1880 3466 -0928
Cl 0000 3798 2342
Al 0000 -3614 0169
Cl -1880 -3466 -0928
Cl 1880 -3466 -0928
Cl 0000 -3798 2342
N 0000 -5757 -0124C 0000 -6214 -1385
C 0000 -7574 -1652N 0000 -8490 -0683
C 0000 -8029 0564C 0000 -6669 0855
H 0000 -5480 -2178H 0000 -7932 -2675
H 0000 -8758 1365
H 0000 -6298 1870N 0000 5757 -0124
C 0000 6669 0855C 0000 8029 0564
N 0000 8490 -0683C 0000 7574 -1652
C 0000 6214 -1385H 0000 6298 1870
H 0000 8758 1365H 0000 7932 -2675
H 0000 5480 -2178
e) (AlCl ) (pyz)3 2 3
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X Y Z
N -1379 0020 -0102
C -0677 1160 -0103
C 0709 1140 -0105
N 1379 -0020 -0102
C 0677 -1160 -0103
C -0709 -1140 -0105
H -1235 2087 -0110
H 1287 2053 -0119
H 1235 -2087 -0110
H -1287 -2053 -0119
Al 3450 0002 -0008
Br 3740 0589 2188
Br 4004 -2153 -0570
Br 3945 1626 -1551
Al -3450 -0002 -0008
Br -3945 -1626 -1551
Br -3740 -0589 2188
Br -4004 2154 -0570
X Y Z
C -4242 0080 -0114
C -3526 1271 -0114
C -2143 1223 -0113
N -1471 0057 -0111
C -2164 -1098 -0113
C -3546 -1123 -0113
H -4026 2230 -0117
H -1539 2120 -0119
H -1577 -2007 -0122
H -4062 -2074 -0116
H -5325 0089 -0116
Al 0541 -0001 0004
Br 0905 -0462 2232
Br 1115 -1718 -1426
Br 1224 2097 -0672
f) AlBr Py3middot
g) AlBr pyz3middot
h) AlBr pyz AlBr3 3middot middot
X Y Z
N 4244 0081 -0125
C 3556 -1060 -0119
C 2169 -1090 -0114
N 1466 0054 -0112
C 2146 1211 -0119
C 3534 1208 -0125
H 4123 -1983 -0121
H 1610 -2016 -0119
H 1565 2123 -0126
H 4082 2142 -0132
Al -0567 -0003 0007
Br -0887 -0431 2243
Br -1216 2091 -0699
Br -1109 -1740 -1402
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X Y Z
N -4996 -0097 0013
C -4277 0761 0737
C -2890 0750 0739
N -2204 -0137 0005
C -2917 -1000 -0728
C -4307 -0970 -0716
H -4819 1482 1338
H -2320 1449 1334
H -2364 -1716 -1319
H -4872 -1676 -1314
Al 0000 0000 -0012
Br 0000 0000 2348
Br 0243 -2033 -1182
Br -0243 2033 -1182
N 2204 0137 0005
C 2917 1000 -0728
C 4307 0970 -0716
N 4996 0097 0013
C 4277 -0761 0737C 2890 -0750 0739
H 2364 1716 -1319H 4872 1676 -1314
H 4819 -1482 1338H 2320 -1449 1334
i) AlBr (pyz)3 2
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X Y Z
N -1391 0048 -0040
C -0646 0600 -1003
C 0739 0552 -0962
N 1391 -0048 0040
C 0646 -0600 1003
C -0739 -0552 0962
H -1169 1088 -1813
H 1332 0999 -1747
H 1169 -1087 1813
H -1332 -0999 1747
Al 3649 0031 0042
Br 3785 -1446 1868
Br 3615 -0823 -2153
Br 3424 2342 0420
Al -3649 -0031 -0042
Br -3424 -2342 -0421
Br -3615 0822 2153
Br -3785 1446 -1867
N -5829 -0094 0032
C -6572 -1191 -0152
C -7961 -1130 -0096
N -8617 0003 0138
C -7867 1090 0320
C -6482 1054 0269
H -6046 -2115 -0341
H -8551 -2026 -0247
H -8382 2024 0513
H -5887 1943 0421
N 5829 0094 -0032
C 6572 1191 0151
C 7961 1130 0096
N 8617 -0003 -0138
C 7867 -1091 -0320
C 6482 -1054 -0269
H 6046 2115 0341
H 8552 2026 0247
H 8382 -2024 -0513
H 5887 -1943 -0420
j) (AlBr ) (pyz)3 2 3
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X Y Z
N 1382 -0013 -0121
C 0682 -1156 -0119
C -0703 -1142 -0120
N -1382 0013 -0121
C -0682 1156 -0119
C 0703 1142 -0120
H 1241 -2082 -0128
H -1277 -2059 -0134
H -1241 2082 -0128
H 1277 2059 -0134
Al -3470 -0006 -0020
I -3767 -0416 2451
I -4124 2286 -0857
I -4054 -1937 -1541
Al 3470 0006 -0020
I 4054 1937 -1541
I 3767 0416 2451
I 4124 -2286 -0857
X Y Z
N -1808 -0040 0000
Al 0220 0038 0000
I 0828 -1193 2134
I 0828 2503 0000
I 0828 -1193 -2134
C -4570 -0274 0000
C -2392 -1255 0000
C -2585 1057 0000
C -3967 0977 0000
C -3765 -1408 0000
H -1727 -2108 0000
H -2066 2007 0000
H -4553 1886 0000
H -4189 -2403 0000
H -5649 -0366 0000
X Y Z
N -4439 0000 -1124
C -3756 1133 -0975
C -2400 1149 -0679
N -1722 0000 -0532
C -2400 -1149 -0679
C -3756 -1133 -0975
H -4299 2063 -1094
H -1843 2070 -0567
H -1843 -2070 -0567
H -4299 -2063 -1094
Al 0249 0000 0041
I 0022 0000 2561
I 1178 -2136 -0957
I 1178 2136 -0957
k) AlI Py3middot
l) AlI pyz3middot
m) AlI pyz AlI3 3middot middot
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X Y Z
N -5010 0212 -0396
C -4286 -0860 -0720
C -2910 -0902 -0560
N -2236 0146 -0063
C -2954 1226 0263
C -4335 1248 0092
H -4816 -1716 -1121
H -2338 -1779 -0827
H -2416 2073 0664
H -4902 2132 0361
Al 0000 0000 0059
I 0000 0000 -2545
I 0252 2176 1448
I -0252 -2176 1448
N 2236 -0146 -0063
C 2954 -1226 0263
C 4335 -1248 0092
N 5010 -0212 -0396
C 4286 0860 -0720
C 2910 0902 -0560
H 2416 -2073 0664
H 4902 -2132 0361
H 4816 1716 -1121
H 2338 1779 -0827
n) AlI (pyz)3 2
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o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
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S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
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d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
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e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
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f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
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i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
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j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
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X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
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S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
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S6
Table S2 Comparison of theoretically predicted and experimental bond distances (in angstroms)
and bond angles (in degrees)
Compound Method rM-N rM-Х ltN-M-X ltX-M-X
AlCl3∙pyz B3LYP 2028 2134-2138 1019-1028 1151-1162
AlCl3∙pyzAlCl3 B3LYP 2063 21262131 1002-1016 1159-1172
pyz∙AlCl3∙pyz B3LYP 2182 2187 878-922 1195-1210
pyz∙AlCl3∙pyz∙AlCl3∙pyz B3LYP 21632228 2181-2182 880-929 1190-1204
AlBr3∙pyz B3LYP 2037 2299-2303 1016-1038 1150-1156
AlBr3∙pyzAlBr3 B3LYP 2074 2292-2295 999-1027 1158-1166
AlBr3∙pyzAlBr3 (1) X-ray 1999 2247-2267 10085-10443 1134-1169
pyz∙AlBr3∙pyz B3LYP 2208 2359-2361 874-930 1197-1205
pyz∙AlBr3∙pyz∙AlBr3∙pyz B3LYP 2182 2259 2352-2355 884-896 1198-1203
(AlBr3∙pyz)infin (3) X-ray 2133 2310-2326 864-934 1160-1281
AlI3∙pyz B3LYP 2053 2530-2534 1011-1043 1148-1152
AlI3∙pyzAlI3 B3LYP 2090 2522-2526 996-1035 1157-1162
pyz∙AlI3∙pyz B3LYP 2242 2244 2594-2603 867-940 1150-1226
pyz∙AlI3∙pyz∙AlI3∙pyz B3LYP 2215 2330 2586-2591 864-953 1184-1207
GaCl3∙pyz B3LYP 2096 2180-2184 1016-1018 1155-1171
GaCl3∙pyzGaCl3 B3LYP 2141 2173-2177 1000-1004 1163-1180
GaCl3∙pyzGaCl3 (2) X-ray 2044 2135-2147 1016-1034 1130-1169
pyz∙GaCl3∙pyz B3LYP 2276 2223-2224 881-919 1196-1208
pyz∙GaCl3∙pyz∙GaCl3∙pyz B3LYP 2243 2336 2218-2219 867-934 1192-1203
(GaCl3∙pyz)infin (4) X-ray 2203 2174-2186 875-9216 1173-1254
GaBr3∙pyz B3LYP 2113 2334-2337 1011-1026 1154-1165
GaBr3∙pyzGaBr3 B3LYP 2161 2327-2330 994-1014 1162-1175
pyz∙GaBr3∙pyz B3LYP 2326 2377-2378 877-925 1197-1206
pyz∙GaBr3∙pyz∙GaBr3∙pyz B3LYP 2277 2416 2371-2373 859-942 1193-1204
GaI3pyz B3LYP 2143 2551-2553 1004-1027 1157-1161
GaI3pyz (5) X-ray 2027 2504-2509 1026-1051 1121-1167
GaI3∙pyzGaI3 B3LYP 2193 2542-2547 992-1013 1167
pyz∙GaI3∙pyz B3LYP 2424 2425 2586-2589 876-931 1200
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S7
Table S3 Total energies Eordm0 standard enthalpies Hordm298 (in Hartree) and entropies Sordm298 (in
cal mol-1
K-1
) B3LYPTZVP level of theory
Compound Eordm0 Hordm298 Sordm298
AlCl3∙Py -18717591724 -18716513100 108239
AlCl3∙pyz -18877870231 -18876915220 108056
AlCl3∙pyzAlCl3 -35111580608 -35110489670 148691
AlCl3(pyz)2 -21522048075 -21520251440 136595
(AlCl3)2(pyz)3 -40400023628 -40397248410 209795
AlBr3∙Py -82136228039 -82135155080 115781
AlBr3∙pyz -82296506985 -82295557760 115627
AlBr3∙pyzAlBr3 -161948858137 -161947779010 163708
AlBr3(pyz)2 -84940643503 -84938853240 146622
(AlBr3)2(pyz)3 -167237224514 -167234462290 225077
AlI3∙Py -13844590963 -1384352177 121837
AlI3∙pyz -14004871976 -1400392624 124387
AlI3∙pyzAlI3 -25365599319 -2536452716 175051
AlI3(pyz)2 -16648951507 -1664716600 151946
(AlI3)2(pyz)3 -30653841482 -3065108822 233288
GaCl3∙Py -35541541594 -3554046971 111664
GaCl3∙pyz -3570182340 -3570087489 111512
GaCl3∙pyzGaCl3 -6875949899 -6875842102 156295
GaCl3(pyz)2 -3834596631 -3834417720 141855
(GaCl3)2(pyz)3 -7404787740 -7404511645 217400
GaBr3∙Py -98960303362 -98959236330 119336
GaBr3∙pyz -99120587356 -99119643780 119266
GaBr3∙pyzGaBr3 -195597035548 -195595967440 171477
GaBr3(pyz)2 -101764685552 -101762902200 151269
(GaBr3)2(pyz)3 -200885318973 -200882569600 235047
GaI3Py -30668807732 -3066774365 126040
GaI3pyz -30829096463 -3082815563 126682
GaI3∙pyzGaI3 -59014069503 -5901300666 181996
GaI3(pyz)2 -3347313909 -3347136003 159749
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S8
Table S4 BSSE energies kJ mol-1
B3LYPTZVP level of theory
Compound X=Cl X=Br X=I
AlX3py 74 62 45
AlX3pyz 74 61 38
AlX3∙pyzAlX3 146 123 99
AlX3(pyz)2 113 91 57
(AlX3)2(pyz)3 222 183 135
GaX3py 64 54 39
GaX3pyz 62 52 39
GaX3∙pyzGaX3 119 102 78
GaX3(pyz)2 89 73 52
(GaX3)2(pyz)3 181 151 -
Table S5 Structural and energetic parameters of mixed 21 complexes Standard
dissociation enthalpies ΔdissHordm298 kJ mol-1
and standard dissociation entropies ΔdissSordm298 J mol-1
K-1
B3LYPTZVP level of theory
MX3-pyz-MX3 r(N1-M) r(N2-M) ΔdissHordm298 ΔdissSordm298
AlCl3-pyz-GaCl3 2061 2144 1995 2769
AlCl3-pyz-AlBr3 2062 2075 2130 2821
AlCl3-pyz-GaBr3 2059 2167 1877 2787
GaCl3-pyz-AlBr3 2143 2072 1897 2817
GaCl3-pyz-GaBr3 2138 2164 1643 2778
AlBr3-pyz-GaBr3 2070 2166 1779 2829
Table S6 Summary of the tensimetry experiments performed in the AlBr3-pyz system
Experiment
number
Temperature
range K
Number of
heatingcooling runs
AlBr3pyz
ratio
Chemical composition (mass of
the substance in mg)
Volume
ml
1 291-675 3 11 AlBr3pyz (362) 2740
2 293-649 4 11 AlBr3pyz (455) 3337
3 291-660 3 1303 AlBr3pyz (455) pyz (213) 3060
4 5 21 (AlBr3)2pyz (282) 5550
5 12 2031 AlBr3 (514) pyz (76) 5905
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S9
Table S7 Melting points Energies of the M-N bonds EM-N and melting enthalpies ΔmeltH kJ mol-1
Compound EM-N Tmelt K ΔmeltH
(AlBr3pyz)infin (3) 85 540 643b
(GaCl3pyz)infin (4) 77 461-463 [11]a 470 [12] 127 [12]
b
(GaBr3pyz)infin 64 361-363 [11]a
a synthesis in nonaqueous solutions
b estimated as difference between sublimation and vaporization
enthalpies from tensimetry studies
Figure S7 System for synthesis of complexes 1 2 3 and 4 ndash places for the sealing off А ndash
ampoule with known amount of pyrazine B ndash ampoule with known amount of AlBr3 С ndash
compartment for the introduction of pyz D ndash ampoule for removal of the excess component E ndash
reaction volume F ndash ampoule to remove the synthesized complex G ndash capillary for the mass
spectrometry study
E
Zeolites
To vacuum pump
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S10
Figure S8 Optimized structures and xyz coordinates for considered aluminum compounds
B3LYPTZVP level of theory
X Y Z
N -1377 0012 -0093
C -0683 1157 -0096
C 0702 1145 -0097
N 1377 -0011 -0093
C 0683 -1157 -0096
C -0702 -1145 -0097
H -1248 2080 -0108
H 1279 2060 -0113
H 1248 -2079 -0108
H -1278 -2060 -0112
Al 3437 -0001 0008
Cl 3710 0310 2094
Cl 3911 -1943 -0731
Cl 3895 1657 -1249
Al -3438 0001 0008
Cl -3895 -1654 -1252
Cl -3710 -0314 2093
Cl -3911 1945 -0727
X Y Z
N 3671 0002 -0002
C 2969 -1130 -0018
C 1582 -1142 -0050
N 0895 0011 -0063
C 1589 1159 -0050
C 2977 1138 -0019
H 3524 -2061 -0008
H 1009 -2059 -0075
H 1020 2079 -0074
H 3537 2065 -0009
Al -1131 0001 0002
Cl -1502 -0192 2095
Cl -1643 1895 -0845
Cl -1622 -1719 -1167
X Y Z
C -3663 0001 0000
C -2962 1200 -0018
C -1579 1169 -0053
N -0895 0010 -0067
C -1572 -1153 -0054
C -2954 -1194 -0019
H -3473 2153 -0008
H -0985 2072 -0077
H -0973 -2054 -0080
H -3458 -2150 -0010
H -4746 -0003 0026
Al 1113 0001 0002
Cl 1517 -0174 2095
Cl 1639 -1726 -1149
Cl 1656 1886 -0859
a) AlCl Py3middot
b) AlCl pyz3middot
c) AlCl pyz AlCl3 3middot middot
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X Y Z
N -4969 0006 -0030
C -4247 0810 0750
C -2861 0771 0775
N -2181 -0091 0006
C -2896 -0902 -0781
C -4285 -0844 -0791
H -4786 1510 1378
H -2284 1423 1416
H -2345 -1599 -1396
H -4854 -1507 -1432
Al 0000 0000 0006
Cl 0000 0000 2193
Cl 0164 -1897 -1071
Cl -0164 1897 -1071
N 2181 0091 0007
C 2896 0902 -0781
C 4285 0844 -0791
N 4969 -0006 -0030
C 4247 -0810 0750C 2861 -0771 0775
H 2345 1599 -1396
H 4854 1507 -1432
H 4786 -1511 1378
H 2284 -1423 1416
d) AlCl (pyz)3 2
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X Y Z
N 0000 -1390 0313
C 0000 -0695 1451
C 0000 0695 1451
N 0000 1390 0313
C 0000 0691 -0830
C 0000 -0691 -0830
H 0000 -1258 2374
H 0000 1258 2374
H 0000 1249 -1755
H 0000 -1249 -1755
Al 0000 3614 0169
Cl 1880 3466 -0928
Cl -1880 3466 -0928
Cl 0000 3798 2342
Al 0000 -3614 0169
Cl -1880 -3466 -0928
Cl 1880 -3466 -0928
Cl 0000 -3798 2342
N 0000 -5757 -0124C 0000 -6214 -1385
C 0000 -7574 -1652N 0000 -8490 -0683
C 0000 -8029 0564C 0000 -6669 0855
H 0000 -5480 -2178H 0000 -7932 -2675
H 0000 -8758 1365
H 0000 -6298 1870N 0000 5757 -0124
C 0000 6669 0855C 0000 8029 0564
N 0000 8490 -0683C 0000 7574 -1652
C 0000 6214 -1385H 0000 6298 1870
H 0000 8758 1365H 0000 7932 -2675
H 0000 5480 -2178
e) (AlCl ) (pyz)3 2 3
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X Y Z
N -1379 0020 -0102
C -0677 1160 -0103
C 0709 1140 -0105
N 1379 -0020 -0102
C 0677 -1160 -0103
C -0709 -1140 -0105
H -1235 2087 -0110
H 1287 2053 -0119
H 1235 -2087 -0110
H -1287 -2053 -0119
Al 3450 0002 -0008
Br 3740 0589 2188
Br 4004 -2153 -0570
Br 3945 1626 -1551
Al -3450 -0002 -0008
Br -3945 -1626 -1551
Br -3740 -0589 2188
Br -4004 2154 -0570
X Y Z
C -4242 0080 -0114
C -3526 1271 -0114
C -2143 1223 -0113
N -1471 0057 -0111
C -2164 -1098 -0113
C -3546 -1123 -0113
H -4026 2230 -0117
H -1539 2120 -0119
H -1577 -2007 -0122
H -4062 -2074 -0116
H -5325 0089 -0116
Al 0541 -0001 0004
Br 0905 -0462 2232
Br 1115 -1718 -1426
Br 1224 2097 -0672
f) AlBr Py3middot
g) AlBr pyz3middot
h) AlBr pyz AlBr3 3middot middot
X Y Z
N 4244 0081 -0125
C 3556 -1060 -0119
C 2169 -1090 -0114
N 1466 0054 -0112
C 2146 1211 -0119
C 3534 1208 -0125
H 4123 -1983 -0121
H 1610 -2016 -0119
H 1565 2123 -0126
H 4082 2142 -0132
Al -0567 -0003 0007
Br -0887 -0431 2243
Br -1216 2091 -0699
Br -1109 -1740 -1402
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X Y Z
N -4996 -0097 0013
C -4277 0761 0737
C -2890 0750 0739
N -2204 -0137 0005
C -2917 -1000 -0728
C -4307 -0970 -0716
H -4819 1482 1338
H -2320 1449 1334
H -2364 -1716 -1319
H -4872 -1676 -1314
Al 0000 0000 -0012
Br 0000 0000 2348
Br 0243 -2033 -1182
Br -0243 2033 -1182
N 2204 0137 0005
C 2917 1000 -0728
C 4307 0970 -0716
N 4996 0097 0013
C 4277 -0761 0737C 2890 -0750 0739
H 2364 1716 -1319H 4872 1676 -1314
H 4819 -1482 1338H 2320 -1449 1334
i) AlBr (pyz)3 2
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X Y Z
N -1391 0048 -0040
C -0646 0600 -1003
C 0739 0552 -0962
N 1391 -0048 0040
C 0646 -0600 1003
C -0739 -0552 0962
H -1169 1088 -1813
H 1332 0999 -1747
H 1169 -1087 1813
H -1332 -0999 1747
Al 3649 0031 0042
Br 3785 -1446 1868
Br 3615 -0823 -2153
Br 3424 2342 0420
Al -3649 -0031 -0042
Br -3424 -2342 -0421
Br -3615 0822 2153
Br -3785 1446 -1867
N -5829 -0094 0032
C -6572 -1191 -0152
C -7961 -1130 -0096
N -8617 0003 0138
C -7867 1090 0320
C -6482 1054 0269
H -6046 -2115 -0341
H -8551 -2026 -0247
H -8382 2024 0513
H -5887 1943 0421
N 5829 0094 -0032
C 6572 1191 0151
C 7961 1130 0096
N 8617 -0003 -0138
C 7867 -1091 -0320
C 6482 -1054 -0269
H 6046 2115 0341
H 8552 2026 0247
H 8382 -2024 -0513
H 5887 -1943 -0420
j) (AlBr ) (pyz)3 2 3
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X Y Z
N 1382 -0013 -0121
C 0682 -1156 -0119
C -0703 -1142 -0120
N -1382 0013 -0121
C -0682 1156 -0119
C 0703 1142 -0120
H 1241 -2082 -0128
H -1277 -2059 -0134
H -1241 2082 -0128
H 1277 2059 -0134
Al -3470 -0006 -0020
I -3767 -0416 2451
I -4124 2286 -0857
I -4054 -1937 -1541
Al 3470 0006 -0020
I 4054 1937 -1541
I 3767 0416 2451
I 4124 -2286 -0857
X Y Z
N -1808 -0040 0000
Al 0220 0038 0000
I 0828 -1193 2134
I 0828 2503 0000
I 0828 -1193 -2134
C -4570 -0274 0000
C -2392 -1255 0000
C -2585 1057 0000
C -3967 0977 0000
C -3765 -1408 0000
H -1727 -2108 0000
H -2066 2007 0000
H -4553 1886 0000
H -4189 -2403 0000
H -5649 -0366 0000
X Y Z
N -4439 0000 -1124
C -3756 1133 -0975
C -2400 1149 -0679
N -1722 0000 -0532
C -2400 -1149 -0679
C -3756 -1133 -0975
H -4299 2063 -1094
H -1843 2070 -0567
H -1843 -2070 -0567
H -4299 -2063 -1094
Al 0249 0000 0041
I 0022 0000 2561
I 1178 -2136 -0957
I 1178 2136 -0957
k) AlI Py3middot
l) AlI pyz3middot
m) AlI pyz AlI3 3middot middot
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X Y Z
N -5010 0212 -0396
C -4286 -0860 -0720
C -2910 -0902 -0560
N -2236 0146 -0063
C -2954 1226 0263
C -4335 1248 0092
H -4816 -1716 -1121
H -2338 -1779 -0827
H -2416 2073 0664
H -4902 2132 0361
Al 0000 0000 0059
I 0000 0000 -2545
I 0252 2176 1448
I -0252 -2176 1448
N 2236 -0146 -0063
C 2954 -1226 0263
C 4335 -1248 0092
N 5010 -0212 -0396
C 4286 0860 -0720
C 2910 0902 -0560
H 2416 -2073 0664
H 4902 -2132 0361
H 4816 1716 -1121
H 2338 1779 -0827
n) AlI (pyz)3 2
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o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
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S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
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d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
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S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
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f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
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i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
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j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
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X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
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n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
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Table S3 Total energies Eordm0 standard enthalpies Hordm298 (in Hartree) and entropies Sordm298 (in
cal mol-1
K-1
) B3LYPTZVP level of theory
Compound Eordm0 Hordm298 Sordm298
AlCl3∙Py -18717591724 -18716513100 108239
AlCl3∙pyz -18877870231 -18876915220 108056
AlCl3∙pyzAlCl3 -35111580608 -35110489670 148691
AlCl3(pyz)2 -21522048075 -21520251440 136595
(AlCl3)2(pyz)3 -40400023628 -40397248410 209795
AlBr3∙Py -82136228039 -82135155080 115781
AlBr3∙pyz -82296506985 -82295557760 115627
AlBr3∙pyzAlBr3 -161948858137 -161947779010 163708
AlBr3(pyz)2 -84940643503 -84938853240 146622
(AlBr3)2(pyz)3 -167237224514 -167234462290 225077
AlI3∙Py -13844590963 -1384352177 121837
AlI3∙pyz -14004871976 -1400392624 124387
AlI3∙pyzAlI3 -25365599319 -2536452716 175051
AlI3(pyz)2 -16648951507 -1664716600 151946
(AlI3)2(pyz)3 -30653841482 -3065108822 233288
GaCl3∙Py -35541541594 -3554046971 111664
GaCl3∙pyz -3570182340 -3570087489 111512
GaCl3∙pyzGaCl3 -6875949899 -6875842102 156295
GaCl3(pyz)2 -3834596631 -3834417720 141855
(GaCl3)2(pyz)3 -7404787740 -7404511645 217400
GaBr3∙Py -98960303362 -98959236330 119336
GaBr3∙pyz -99120587356 -99119643780 119266
GaBr3∙pyzGaBr3 -195597035548 -195595967440 171477
GaBr3(pyz)2 -101764685552 -101762902200 151269
(GaBr3)2(pyz)3 -200885318973 -200882569600 235047
GaI3Py -30668807732 -3066774365 126040
GaI3pyz -30829096463 -3082815563 126682
GaI3∙pyzGaI3 -59014069503 -5901300666 181996
GaI3(pyz)2 -3347313909 -3347136003 159749
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Table S4 BSSE energies kJ mol-1
B3LYPTZVP level of theory
Compound X=Cl X=Br X=I
AlX3py 74 62 45
AlX3pyz 74 61 38
AlX3∙pyzAlX3 146 123 99
AlX3(pyz)2 113 91 57
(AlX3)2(pyz)3 222 183 135
GaX3py 64 54 39
GaX3pyz 62 52 39
GaX3∙pyzGaX3 119 102 78
GaX3(pyz)2 89 73 52
(GaX3)2(pyz)3 181 151 -
Table S5 Structural and energetic parameters of mixed 21 complexes Standard
dissociation enthalpies ΔdissHordm298 kJ mol-1
and standard dissociation entropies ΔdissSordm298 J mol-1
K-1
B3LYPTZVP level of theory
MX3-pyz-MX3 r(N1-M) r(N2-M) ΔdissHordm298 ΔdissSordm298
AlCl3-pyz-GaCl3 2061 2144 1995 2769
AlCl3-pyz-AlBr3 2062 2075 2130 2821
AlCl3-pyz-GaBr3 2059 2167 1877 2787
GaCl3-pyz-AlBr3 2143 2072 1897 2817
GaCl3-pyz-GaBr3 2138 2164 1643 2778
AlBr3-pyz-GaBr3 2070 2166 1779 2829
Table S6 Summary of the tensimetry experiments performed in the AlBr3-pyz system
Experiment
number
Temperature
range K
Number of
heatingcooling runs
AlBr3pyz
ratio
Chemical composition (mass of
the substance in mg)
Volume
ml
1 291-675 3 11 AlBr3pyz (362) 2740
2 293-649 4 11 AlBr3pyz (455) 3337
3 291-660 3 1303 AlBr3pyz (455) pyz (213) 3060
4 5 21 (AlBr3)2pyz (282) 5550
5 12 2031 AlBr3 (514) pyz (76) 5905
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S9
Table S7 Melting points Energies of the M-N bonds EM-N and melting enthalpies ΔmeltH kJ mol-1
Compound EM-N Tmelt K ΔmeltH
(AlBr3pyz)infin (3) 85 540 643b
(GaCl3pyz)infin (4) 77 461-463 [11]a 470 [12] 127 [12]
b
(GaBr3pyz)infin 64 361-363 [11]a
a synthesis in nonaqueous solutions
b estimated as difference between sublimation and vaporization
enthalpies from tensimetry studies
Figure S7 System for synthesis of complexes 1 2 3 and 4 ndash places for the sealing off А ndash
ampoule with known amount of pyrazine B ndash ampoule with known amount of AlBr3 С ndash
compartment for the introduction of pyz D ndash ampoule for removal of the excess component E ndash
reaction volume F ndash ampoule to remove the synthesized complex G ndash capillary for the mass
spectrometry study
E
Zeolites
To vacuum pump
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S10
Figure S8 Optimized structures and xyz coordinates for considered aluminum compounds
B3LYPTZVP level of theory
X Y Z
N -1377 0012 -0093
C -0683 1157 -0096
C 0702 1145 -0097
N 1377 -0011 -0093
C 0683 -1157 -0096
C -0702 -1145 -0097
H -1248 2080 -0108
H 1279 2060 -0113
H 1248 -2079 -0108
H -1278 -2060 -0112
Al 3437 -0001 0008
Cl 3710 0310 2094
Cl 3911 -1943 -0731
Cl 3895 1657 -1249
Al -3438 0001 0008
Cl -3895 -1654 -1252
Cl -3710 -0314 2093
Cl -3911 1945 -0727
X Y Z
N 3671 0002 -0002
C 2969 -1130 -0018
C 1582 -1142 -0050
N 0895 0011 -0063
C 1589 1159 -0050
C 2977 1138 -0019
H 3524 -2061 -0008
H 1009 -2059 -0075
H 1020 2079 -0074
H 3537 2065 -0009
Al -1131 0001 0002
Cl -1502 -0192 2095
Cl -1643 1895 -0845
Cl -1622 -1719 -1167
X Y Z
C -3663 0001 0000
C -2962 1200 -0018
C -1579 1169 -0053
N -0895 0010 -0067
C -1572 -1153 -0054
C -2954 -1194 -0019
H -3473 2153 -0008
H -0985 2072 -0077
H -0973 -2054 -0080
H -3458 -2150 -0010
H -4746 -0003 0026
Al 1113 0001 0002
Cl 1517 -0174 2095
Cl 1639 -1726 -1149
Cl 1656 1886 -0859
a) AlCl Py3middot
b) AlCl pyz3middot
c) AlCl pyz AlCl3 3middot middot
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X Y Z
N -4969 0006 -0030
C -4247 0810 0750
C -2861 0771 0775
N -2181 -0091 0006
C -2896 -0902 -0781
C -4285 -0844 -0791
H -4786 1510 1378
H -2284 1423 1416
H -2345 -1599 -1396
H -4854 -1507 -1432
Al 0000 0000 0006
Cl 0000 0000 2193
Cl 0164 -1897 -1071
Cl -0164 1897 -1071
N 2181 0091 0007
C 2896 0902 -0781
C 4285 0844 -0791
N 4969 -0006 -0030
C 4247 -0810 0750C 2861 -0771 0775
H 2345 1599 -1396
H 4854 1507 -1432
H 4786 -1511 1378
H 2284 -1423 1416
d) AlCl (pyz)3 2
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X Y Z
N 0000 -1390 0313
C 0000 -0695 1451
C 0000 0695 1451
N 0000 1390 0313
C 0000 0691 -0830
C 0000 -0691 -0830
H 0000 -1258 2374
H 0000 1258 2374
H 0000 1249 -1755
H 0000 -1249 -1755
Al 0000 3614 0169
Cl 1880 3466 -0928
Cl -1880 3466 -0928
Cl 0000 3798 2342
Al 0000 -3614 0169
Cl -1880 -3466 -0928
Cl 1880 -3466 -0928
Cl 0000 -3798 2342
N 0000 -5757 -0124C 0000 -6214 -1385
C 0000 -7574 -1652N 0000 -8490 -0683
C 0000 -8029 0564C 0000 -6669 0855
H 0000 -5480 -2178H 0000 -7932 -2675
H 0000 -8758 1365
H 0000 -6298 1870N 0000 5757 -0124
C 0000 6669 0855C 0000 8029 0564
N 0000 8490 -0683C 0000 7574 -1652
C 0000 6214 -1385H 0000 6298 1870
H 0000 8758 1365H 0000 7932 -2675
H 0000 5480 -2178
e) (AlCl ) (pyz)3 2 3
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X Y Z
N -1379 0020 -0102
C -0677 1160 -0103
C 0709 1140 -0105
N 1379 -0020 -0102
C 0677 -1160 -0103
C -0709 -1140 -0105
H -1235 2087 -0110
H 1287 2053 -0119
H 1235 -2087 -0110
H -1287 -2053 -0119
Al 3450 0002 -0008
Br 3740 0589 2188
Br 4004 -2153 -0570
Br 3945 1626 -1551
Al -3450 -0002 -0008
Br -3945 -1626 -1551
Br -3740 -0589 2188
Br -4004 2154 -0570
X Y Z
C -4242 0080 -0114
C -3526 1271 -0114
C -2143 1223 -0113
N -1471 0057 -0111
C -2164 -1098 -0113
C -3546 -1123 -0113
H -4026 2230 -0117
H -1539 2120 -0119
H -1577 -2007 -0122
H -4062 -2074 -0116
H -5325 0089 -0116
Al 0541 -0001 0004
Br 0905 -0462 2232
Br 1115 -1718 -1426
Br 1224 2097 -0672
f) AlBr Py3middot
g) AlBr pyz3middot
h) AlBr pyz AlBr3 3middot middot
X Y Z
N 4244 0081 -0125
C 3556 -1060 -0119
C 2169 -1090 -0114
N 1466 0054 -0112
C 2146 1211 -0119
C 3534 1208 -0125
H 4123 -1983 -0121
H 1610 -2016 -0119
H 1565 2123 -0126
H 4082 2142 -0132
Al -0567 -0003 0007
Br -0887 -0431 2243
Br -1216 2091 -0699
Br -1109 -1740 -1402
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X Y Z
N -4996 -0097 0013
C -4277 0761 0737
C -2890 0750 0739
N -2204 -0137 0005
C -2917 -1000 -0728
C -4307 -0970 -0716
H -4819 1482 1338
H -2320 1449 1334
H -2364 -1716 -1319
H -4872 -1676 -1314
Al 0000 0000 -0012
Br 0000 0000 2348
Br 0243 -2033 -1182
Br -0243 2033 -1182
N 2204 0137 0005
C 2917 1000 -0728
C 4307 0970 -0716
N 4996 0097 0013
C 4277 -0761 0737C 2890 -0750 0739
H 2364 1716 -1319H 4872 1676 -1314
H 4819 -1482 1338H 2320 -1449 1334
i) AlBr (pyz)3 2
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X Y Z
N -1391 0048 -0040
C -0646 0600 -1003
C 0739 0552 -0962
N 1391 -0048 0040
C 0646 -0600 1003
C -0739 -0552 0962
H -1169 1088 -1813
H 1332 0999 -1747
H 1169 -1087 1813
H -1332 -0999 1747
Al 3649 0031 0042
Br 3785 -1446 1868
Br 3615 -0823 -2153
Br 3424 2342 0420
Al -3649 -0031 -0042
Br -3424 -2342 -0421
Br -3615 0822 2153
Br -3785 1446 -1867
N -5829 -0094 0032
C -6572 -1191 -0152
C -7961 -1130 -0096
N -8617 0003 0138
C -7867 1090 0320
C -6482 1054 0269
H -6046 -2115 -0341
H -8551 -2026 -0247
H -8382 2024 0513
H -5887 1943 0421
N 5829 0094 -0032
C 6572 1191 0151
C 7961 1130 0096
N 8617 -0003 -0138
C 7867 -1091 -0320
C 6482 -1054 -0269
H 6046 2115 0341
H 8552 2026 0247
H 8382 -2024 -0513
H 5887 -1943 -0420
j) (AlBr ) (pyz)3 2 3
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X Y Z
N 1382 -0013 -0121
C 0682 -1156 -0119
C -0703 -1142 -0120
N -1382 0013 -0121
C -0682 1156 -0119
C 0703 1142 -0120
H 1241 -2082 -0128
H -1277 -2059 -0134
H -1241 2082 -0128
H 1277 2059 -0134
Al -3470 -0006 -0020
I -3767 -0416 2451
I -4124 2286 -0857
I -4054 -1937 -1541
Al 3470 0006 -0020
I 4054 1937 -1541
I 3767 0416 2451
I 4124 -2286 -0857
X Y Z
N -1808 -0040 0000
Al 0220 0038 0000
I 0828 -1193 2134
I 0828 2503 0000
I 0828 -1193 -2134
C -4570 -0274 0000
C -2392 -1255 0000
C -2585 1057 0000
C -3967 0977 0000
C -3765 -1408 0000
H -1727 -2108 0000
H -2066 2007 0000
H -4553 1886 0000
H -4189 -2403 0000
H -5649 -0366 0000
X Y Z
N -4439 0000 -1124
C -3756 1133 -0975
C -2400 1149 -0679
N -1722 0000 -0532
C -2400 -1149 -0679
C -3756 -1133 -0975
H -4299 2063 -1094
H -1843 2070 -0567
H -1843 -2070 -0567
H -4299 -2063 -1094
Al 0249 0000 0041
I 0022 0000 2561
I 1178 -2136 -0957
I 1178 2136 -0957
k) AlI Py3middot
l) AlI pyz3middot
m) AlI pyz AlI3 3middot middot
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X Y Z
N -5010 0212 -0396
C -4286 -0860 -0720
C -2910 -0902 -0560
N -2236 0146 -0063
C -2954 1226 0263
C -4335 1248 0092
H -4816 -1716 -1121
H -2338 -1779 -0827
H -2416 2073 0664
H -4902 2132 0361
Al 0000 0000 0059
I 0000 0000 -2545
I 0252 2176 1448
I -0252 -2176 1448
N 2236 -0146 -0063
C 2954 -1226 0263
C 4335 -1248 0092
N 5010 -0212 -0396
C 4286 0860 -0720
C 2910 0902 -0560
H 2416 -2073 0664
H 4902 -2132 0361
H 4816 1716 -1121
H 2338 1779 -0827
n) AlI (pyz)3 2
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o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
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S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
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S20
d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
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S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
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f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
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i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
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S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
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X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
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n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
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S8
Table S4 BSSE energies kJ mol-1
B3LYPTZVP level of theory
Compound X=Cl X=Br X=I
AlX3py 74 62 45
AlX3pyz 74 61 38
AlX3∙pyzAlX3 146 123 99
AlX3(pyz)2 113 91 57
(AlX3)2(pyz)3 222 183 135
GaX3py 64 54 39
GaX3pyz 62 52 39
GaX3∙pyzGaX3 119 102 78
GaX3(pyz)2 89 73 52
(GaX3)2(pyz)3 181 151 -
Table S5 Structural and energetic parameters of mixed 21 complexes Standard
dissociation enthalpies ΔdissHordm298 kJ mol-1
and standard dissociation entropies ΔdissSordm298 J mol-1
K-1
B3LYPTZVP level of theory
MX3-pyz-MX3 r(N1-M) r(N2-M) ΔdissHordm298 ΔdissSordm298
AlCl3-pyz-GaCl3 2061 2144 1995 2769
AlCl3-pyz-AlBr3 2062 2075 2130 2821
AlCl3-pyz-GaBr3 2059 2167 1877 2787
GaCl3-pyz-AlBr3 2143 2072 1897 2817
GaCl3-pyz-GaBr3 2138 2164 1643 2778
AlBr3-pyz-GaBr3 2070 2166 1779 2829
Table S6 Summary of the tensimetry experiments performed in the AlBr3-pyz system
Experiment
number
Temperature
range K
Number of
heatingcooling runs
AlBr3pyz
ratio
Chemical composition (mass of
the substance in mg)
Volume
ml
1 291-675 3 11 AlBr3pyz (362) 2740
2 293-649 4 11 AlBr3pyz (455) 3337
3 291-660 3 1303 AlBr3pyz (455) pyz (213) 3060
4 5 21 (AlBr3)2pyz (282) 5550
5 12 2031 AlBr3 (514) pyz (76) 5905
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S9
Table S7 Melting points Energies of the M-N bonds EM-N and melting enthalpies ΔmeltH kJ mol-1
Compound EM-N Tmelt K ΔmeltH
(AlBr3pyz)infin (3) 85 540 643b
(GaCl3pyz)infin (4) 77 461-463 [11]a 470 [12] 127 [12]
b
(GaBr3pyz)infin 64 361-363 [11]a
a synthesis in nonaqueous solutions
b estimated as difference between sublimation and vaporization
enthalpies from tensimetry studies
Figure S7 System for synthesis of complexes 1 2 3 and 4 ndash places for the sealing off А ndash
ampoule with known amount of pyrazine B ndash ampoule with known amount of AlBr3 С ndash
compartment for the introduction of pyz D ndash ampoule for removal of the excess component E ndash
reaction volume F ndash ampoule to remove the synthesized complex G ndash capillary for the mass
spectrometry study
E
Zeolites
To vacuum pump
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S10
Figure S8 Optimized structures and xyz coordinates for considered aluminum compounds
B3LYPTZVP level of theory
X Y Z
N -1377 0012 -0093
C -0683 1157 -0096
C 0702 1145 -0097
N 1377 -0011 -0093
C 0683 -1157 -0096
C -0702 -1145 -0097
H -1248 2080 -0108
H 1279 2060 -0113
H 1248 -2079 -0108
H -1278 -2060 -0112
Al 3437 -0001 0008
Cl 3710 0310 2094
Cl 3911 -1943 -0731
Cl 3895 1657 -1249
Al -3438 0001 0008
Cl -3895 -1654 -1252
Cl -3710 -0314 2093
Cl -3911 1945 -0727
X Y Z
N 3671 0002 -0002
C 2969 -1130 -0018
C 1582 -1142 -0050
N 0895 0011 -0063
C 1589 1159 -0050
C 2977 1138 -0019
H 3524 -2061 -0008
H 1009 -2059 -0075
H 1020 2079 -0074
H 3537 2065 -0009
Al -1131 0001 0002
Cl -1502 -0192 2095
Cl -1643 1895 -0845
Cl -1622 -1719 -1167
X Y Z
C -3663 0001 0000
C -2962 1200 -0018
C -1579 1169 -0053
N -0895 0010 -0067
C -1572 -1153 -0054
C -2954 -1194 -0019
H -3473 2153 -0008
H -0985 2072 -0077
H -0973 -2054 -0080
H -3458 -2150 -0010
H -4746 -0003 0026
Al 1113 0001 0002
Cl 1517 -0174 2095
Cl 1639 -1726 -1149
Cl 1656 1886 -0859
a) AlCl Py3middot
b) AlCl pyz3middot
c) AlCl pyz AlCl3 3middot middot
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X Y Z
N -4969 0006 -0030
C -4247 0810 0750
C -2861 0771 0775
N -2181 -0091 0006
C -2896 -0902 -0781
C -4285 -0844 -0791
H -4786 1510 1378
H -2284 1423 1416
H -2345 -1599 -1396
H -4854 -1507 -1432
Al 0000 0000 0006
Cl 0000 0000 2193
Cl 0164 -1897 -1071
Cl -0164 1897 -1071
N 2181 0091 0007
C 2896 0902 -0781
C 4285 0844 -0791
N 4969 -0006 -0030
C 4247 -0810 0750C 2861 -0771 0775
H 2345 1599 -1396
H 4854 1507 -1432
H 4786 -1511 1378
H 2284 -1423 1416
d) AlCl (pyz)3 2
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S12
X Y Z
N 0000 -1390 0313
C 0000 -0695 1451
C 0000 0695 1451
N 0000 1390 0313
C 0000 0691 -0830
C 0000 -0691 -0830
H 0000 -1258 2374
H 0000 1258 2374
H 0000 1249 -1755
H 0000 -1249 -1755
Al 0000 3614 0169
Cl 1880 3466 -0928
Cl -1880 3466 -0928
Cl 0000 3798 2342
Al 0000 -3614 0169
Cl -1880 -3466 -0928
Cl 1880 -3466 -0928
Cl 0000 -3798 2342
N 0000 -5757 -0124C 0000 -6214 -1385
C 0000 -7574 -1652N 0000 -8490 -0683
C 0000 -8029 0564C 0000 -6669 0855
H 0000 -5480 -2178H 0000 -7932 -2675
H 0000 -8758 1365
H 0000 -6298 1870N 0000 5757 -0124
C 0000 6669 0855C 0000 8029 0564
N 0000 8490 -0683C 0000 7574 -1652
C 0000 6214 -1385H 0000 6298 1870
H 0000 8758 1365H 0000 7932 -2675
H 0000 5480 -2178
e) (AlCl ) (pyz)3 2 3
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S13
X Y Z
N -1379 0020 -0102
C -0677 1160 -0103
C 0709 1140 -0105
N 1379 -0020 -0102
C 0677 -1160 -0103
C -0709 -1140 -0105
H -1235 2087 -0110
H 1287 2053 -0119
H 1235 -2087 -0110
H -1287 -2053 -0119
Al 3450 0002 -0008
Br 3740 0589 2188
Br 4004 -2153 -0570
Br 3945 1626 -1551
Al -3450 -0002 -0008
Br -3945 -1626 -1551
Br -3740 -0589 2188
Br -4004 2154 -0570
X Y Z
C -4242 0080 -0114
C -3526 1271 -0114
C -2143 1223 -0113
N -1471 0057 -0111
C -2164 -1098 -0113
C -3546 -1123 -0113
H -4026 2230 -0117
H -1539 2120 -0119
H -1577 -2007 -0122
H -4062 -2074 -0116
H -5325 0089 -0116
Al 0541 -0001 0004
Br 0905 -0462 2232
Br 1115 -1718 -1426
Br 1224 2097 -0672
f) AlBr Py3middot
g) AlBr pyz3middot
h) AlBr pyz AlBr3 3middot middot
X Y Z
N 4244 0081 -0125
C 3556 -1060 -0119
C 2169 -1090 -0114
N 1466 0054 -0112
C 2146 1211 -0119
C 3534 1208 -0125
H 4123 -1983 -0121
H 1610 -2016 -0119
H 1565 2123 -0126
H 4082 2142 -0132
Al -0567 -0003 0007
Br -0887 -0431 2243
Br -1216 2091 -0699
Br -1109 -1740 -1402
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X Y Z
N -4996 -0097 0013
C -4277 0761 0737
C -2890 0750 0739
N -2204 -0137 0005
C -2917 -1000 -0728
C -4307 -0970 -0716
H -4819 1482 1338
H -2320 1449 1334
H -2364 -1716 -1319
H -4872 -1676 -1314
Al 0000 0000 -0012
Br 0000 0000 2348
Br 0243 -2033 -1182
Br -0243 2033 -1182
N 2204 0137 0005
C 2917 1000 -0728
C 4307 0970 -0716
N 4996 0097 0013
C 4277 -0761 0737C 2890 -0750 0739
H 2364 1716 -1319H 4872 1676 -1314
H 4819 -1482 1338H 2320 -1449 1334
i) AlBr (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S15
X Y Z
N -1391 0048 -0040
C -0646 0600 -1003
C 0739 0552 -0962
N 1391 -0048 0040
C 0646 -0600 1003
C -0739 -0552 0962
H -1169 1088 -1813
H 1332 0999 -1747
H 1169 -1087 1813
H -1332 -0999 1747
Al 3649 0031 0042
Br 3785 -1446 1868
Br 3615 -0823 -2153
Br 3424 2342 0420
Al -3649 -0031 -0042
Br -3424 -2342 -0421
Br -3615 0822 2153
Br -3785 1446 -1867
N -5829 -0094 0032
C -6572 -1191 -0152
C -7961 -1130 -0096
N -8617 0003 0138
C -7867 1090 0320
C -6482 1054 0269
H -6046 -2115 -0341
H -8551 -2026 -0247
H -8382 2024 0513
H -5887 1943 0421
N 5829 0094 -0032
C 6572 1191 0151
C 7961 1130 0096
N 8617 -0003 -0138
C 7867 -1091 -0320
C 6482 -1054 -0269
H 6046 2115 0341
H 8552 2026 0247
H 8382 -2024 -0513
H 5887 -1943 -0420
j) (AlBr ) (pyz)3 2 3
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S16
X Y Z
N 1382 -0013 -0121
C 0682 -1156 -0119
C -0703 -1142 -0120
N -1382 0013 -0121
C -0682 1156 -0119
C 0703 1142 -0120
H 1241 -2082 -0128
H -1277 -2059 -0134
H -1241 2082 -0128
H 1277 2059 -0134
Al -3470 -0006 -0020
I -3767 -0416 2451
I -4124 2286 -0857
I -4054 -1937 -1541
Al 3470 0006 -0020
I 4054 1937 -1541
I 3767 0416 2451
I 4124 -2286 -0857
X Y Z
N -1808 -0040 0000
Al 0220 0038 0000
I 0828 -1193 2134
I 0828 2503 0000
I 0828 -1193 -2134
C -4570 -0274 0000
C -2392 -1255 0000
C -2585 1057 0000
C -3967 0977 0000
C -3765 -1408 0000
H -1727 -2108 0000
H -2066 2007 0000
H -4553 1886 0000
H -4189 -2403 0000
H -5649 -0366 0000
X Y Z
N -4439 0000 -1124
C -3756 1133 -0975
C -2400 1149 -0679
N -1722 0000 -0532
C -2400 -1149 -0679
C -3756 -1133 -0975
H -4299 2063 -1094
H -1843 2070 -0567
H -1843 -2070 -0567
H -4299 -2063 -1094
Al 0249 0000 0041
I 0022 0000 2561
I 1178 -2136 -0957
I 1178 2136 -0957
k) AlI Py3middot
l) AlI pyz3middot
m) AlI pyz AlI3 3middot middot
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S17
X Y Z
N -5010 0212 -0396
C -4286 -0860 -0720
C -2910 -0902 -0560
N -2236 0146 -0063
C -2954 1226 0263
C -4335 1248 0092
H -4816 -1716 -1121
H -2338 -1779 -0827
H -2416 2073 0664
H -4902 2132 0361
Al 0000 0000 0059
I 0000 0000 -2545
I 0252 2176 1448
I -0252 -2176 1448
N 2236 -0146 -0063
C 2954 -1226 0263
C 4335 -1248 0092
N 5010 -0212 -0396
C 4286 0860 -0720
C 2910 0902 -0560
H 2416 -2073 0664
H 4902 -2132 0361
H 4816 1716 -1121
H 2338 1779 -0827
n) AlI (pyz)3 2
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S18
o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S20
d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S22
f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S23
i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
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X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
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n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
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Table S7 Melting points Energies of the M-N bonds EM-N and melting enthalpies ΔmeltH kJ mol-1
Compound EM-N Tmelt K ΔmeltH
(AlBr3pyz)infin (3) 85 540 643b
(GaCl3pyz)infin (4) 77 461-463 [11]a 470 [12] 127 [12]
b
(GaBr3pyz)infin 64 361-363 [11]a
a synthesis in nonaqueous solutions
b estimated as difference between sublimation and vaporization
enthalpies from tensimetry studies
Figure S7 System for synthesis of complexes 1 2 3 and 4 ndash places for the sealing off А ndash
ampoule with known amount of pyrazine B ndash ampoule with known amount of AlBr3 С ndash
compartment for the introduction of pyz D ndash ampoule for removal of the excess component E ndash
reaction volume F ndash ampoule to remove the synthesized complex G ndash capillary for the mass
spectrometry study
E
Zeolites
To vacuum pump
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S10
Figure S8 Optimized structures and xyz coordinates for considered aluminum compounds
B3LYPTZVP level of theory
X Y Z
N -1377 0012 -0093
C -0683 1157 -0096
C 0702 1145 -0097
N 1377 -0011 -0093
C 0683 -1157 -0096
C -0702 -1145 -0097
H -1248 2080 -0108
H 1279 2060 -0113
H 1248 -2079 -0108
H -1278 -2060 -0112
Al 3437 -0001 0008
Cl 3710 0310 2094
Cl 3911 -1943 -0731
Cl 3895 1657 -1249
Al -3438 0001 0008
Cl -3895 -1654 -1252
Cl -3710 -0314 2093
Cl -3911 1945 -0727
X Y Z
N 3671 0002 -0002
C 2969 -1130 -0018
C 1582 -1142 -0050
N 0895 0011 -0063
C 1589 1159 -0050
C 2977 1138 -0019
H 3524 -2061 -0008
H 1009 -2059 -0075
H 1020 2079 -0074
H 3537 2065 -0009
Al -1131 0001 0002
Cl -1502 -0192 2095
Cl -1643 1895 -0845
Cl -1622 -1719 -1167
X Y Z
C -3663 0001 0000
C -2962 1200 -0018
C -1579 1169 -0053
N -0895 0010 -0067
C -1572 -1153 -0054
C -2954 -1194 -0019
H -3473 2153 -0008
H -0985 2072 -0077
H -0973 -2054 -0080
H -3458 -2150 -0010
H -4746 -0003 0026
Al 1113 0001 0002
Cl 1517 -0174 2095
Cl 1639 -1726 -1149
Cl 1656 1886 -0859
a) AlCl Py3middot
b) AlCl pyz3middot
c) AlCl pyz AlCl3 3middot middot
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
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X Y Z
N -4969 0006 -0030
C -4247 0810 0750
C -2861 0771 0775
N -2181 -0091 0006
C -2896 -0902 -0781
C -4285 -0844 -0791
H -4786 1510 1378
H -2284 1423 1416
H -2345 -1599 -1396
H -4854 -1507 -1432
Al 0000 0000 0006
Cl 0000 0000 2193
Cl 0164 -1897 -1071
Cl -0164 1897 -1071
N 2181 0091 0007
C 2896 0902 -0781
C 4285 0844 -0791
N 4969 -0006 -0030
C 4247 -0810 0750C 2861 -0771 0775
H 2345 1599 -1396
H 4854 1507 -1432
H 4786 -1511 1378
H 2284 -1423 1416
d) AlCl (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
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X Y Z
N 0000 -1390 0313
C 0000 -0695 1451
C 0000 0695 1451
N 0000 1390 0313
C 0000 0691 -0830
C 0000 -0691 -0830
H 0000 -1258 2374
H 0000 1258 2374
H 0000 1249 -1755
H 0000 -1249 -1755
Al 0000 3614 0169
Cl 1880 3466 -0928
Cl -1880 3466 -0928
Cl 0000 3798 2342
Al 0000 -3614 0169
Cl -1880 -3466 -0928
Cl 1880 -3466 -0928
Cl 0000 -3798 2342
N 0000 -5757 -0124C 0000 -6214 -1385
C 0000 -7574 -1652N 0000 -8490 -0683
C 0000 -8029 0564C 0000 -6669 0855
H 0000 -5480 -2178H 0000 -7932 -2675
H 0000 -8758 1365
H 0000 -6298 1870N 0000 5757 -0124
C 0000 6669 0855C 0000 8029 0564
N 0000 8490 -0683C 0000 7574 -1652
C 0000 6214 -1385H 0000 6298 1870
H 0000 8758 1365H 0000 7932 -2675
H 0000 5480 -2178
e) (AlCl ) (pyz)3 2 3
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S13
X Y Z
N -1379 0020 -0102
C -0677 1160 -0103
C 0709 1140 -0105
N 1379 -0020 -0102
C 0677 -1160 -0103
C -0709 -1140 -0105
H -1235 2087 -0110
H 1287 2053 -0119
H 1235 -2087 -0110
H -1287 -2053 -0119
Al 3450 0002 -0008
Br 3740 0589 2188
Br 4004 -2153 -0570
Br 3945 1626 -1551
Al -3450 -0002 -0008
Br -3945 -1626 -1551
Br -3740 -0589 2188
Br -4004 2154 -0570
X Y Z
C -4242 0080 -0114
C -3526 1271 -0114
C -2143 1223 -0113
N -1471 0057 -0111
C -2164 -1098 -0113
C -3546 -1123 -0113
H -4026 2230 -0117
H -1539 2120 -0119
H -1577 -2007 -0122
H -4062 -2074 -0116
H -5325 0089 -0116
Al 0541 -0001 0004
Br 0905 -0462 2232
Br 1115 -1718 -1426
Br 1224 2097 -0672
f) AlBr Py3middot
g) AlBr pyz3middot
h) AlBr pyz AlBr3 3middot middot
X Y Z
N 4244 0081 -0125
C 3556 -1060 -0119
C 2169 -1090 -0114
N 1466 0054 -0112
C 2146 1211 -0119
C 3534 1208 -0125
H 4123 -1983 -0121
H 1610 -2016 -0119
H 1565 2123 -0126
H 4082 2142 -0132
Al -0567 -0003 0007
Br -0887 -0431 2243
Br -1216 2091 -0699
Br -1109 -1740 -1402
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S14
X Y Z
N -4996 -0097 0013
C -4277 0761 0737
C -2890 0750 0739
N -2204 -0137 0005
C -2917 -1000 -0728
C -4307 -0970 -0716
H -4819 1482 1338
H -2320 1449 1334
H -2364 -1716 -1319
H -4872 -1676 -1314
Al 0000 0000 -0012
Br 0000 0000 2348
Br 0243 -2033 -1182
Br -0243 2033 -1182
N 2204 0137 0005
C 2917 1000 -0728
C 4307 0970 -0716
N 4996 0097 0013
C 4277 -0761 0737C 2890 -0750 0739
H 2364 1716 -1319H 4872 1676 -1314
H 4819 -1482 1338H 2320 -1449 1334
i) AlBr (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S15
X Y Z
N -1391 0048 -0040
C -0646 0600 -1003
C 0739 0552 -0962
N 1391 -0048 0040
C 0646 -0600 1003
C -0739 -0552 0962
H -1169 1088 -1813
H 1332 0999 -1747
H 1169 -1087 1813
H -1332 -0999 1747
Al 3649 0031 0042
Br 3785 -1446 1868
Br 3615 -0823 -2153
Br 3424 2342 0420
Al -3649 -0031 -0042
Br -3424 -2342 -0421
Br -3615 0822 2153
Br -3785 1446 -1867
N -5829 -0094 0032
C -6572 -1191 -0152
C -7961 -1130 -0096
N -8617 0003 0138
C -7867 1090 0320
C -6482 1054 0269
H -6046 -2115 -0341
H -8551 -2026 -0247
H -8382 2024 0513
H -5887 1943 0421
N 5829 0094 -0032
C 6572 1191 0151
C 7961 1130 0096
N 8617 -0003 -0138
C 7867 -1091 -0320
C 6482 -1054 -0269
H 6046 2115 0341
H 8552 2026 0247
H 8382 -2024 -0513
H 5887 -1943 -0420
j) (AlBr ) (pyz)3 2 3
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S16
X Y Z
N 1382 -0013 -0121
C 0682 -1156 -0119
C -0703 -1142 -0120
N -1382 0013 -0121
C -0682 1156 -0119
C 0703 1142 -0120
H 1241 -2082 -0128
H -1277 -2059 -0134
H -1241 2082 -0128
H 1277 2059 -0134
Al -3470 -0006 -0020
I -3767 -0416 2451
I -4124 2286 -0857
I -4054 -1937 -1541
Al 3470 0006 -0020
I 4054 1937 -1541
I 3767 0416 2451
I 4124 -2286 -0857
X Y Z
N -1808 -0040 0000
Al 0220 0038 0000
I 0828 -1193 2134
I 0828 2503 0000
I 0828 -1193 -2134
C -4570 -0274 0000
C -2392 -1255 0000
C -2585 1057 0000
C -3967 0977 0000
C -3765 -1408 0000
H -1727 -2108 0000
H -2066 2007 0000
H -4553 1886 0000
H -4189 -2403 0000
H -5649 -0366 0000
X Y Z
N -4439 0000 -1124
C -3756 1133 -0975
C -2400 1149 -0679
N -1722 0000 -0532
C -2400 -1149 -0679
C -3756 -1133 -0975
H -4299 2063 -1094
H -1843 2070 -0567
H -1843 -2070 -0567
H -4299 -2063 -1094
Al 0249 0000 0041
I 0022 0000 2561
I 1178 -2136 -0957
I 1178 2136 -0957
k) AlI Py3middot
l) AlI pyz3middot
m) AlI pyz AlI3 3middot middot
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S17
X Y Z
N -5010 0212 -0396
C -4286 -0860 -0720
C -2910 -0902 -0560
N -2236 0146 -0063
C -2954 1226 0263
C -4335 1248 0092
H -4816 -1716 -1121
H -2338 -1779 -0827
H -2416 2073 0664
H -4902 2132 0361
Al 0000 0000 0059
I 0000 0000 -2545
I 0252 2176 1448
I -0252 -2176 1448
N 2236 -0146 -0063
C 2954 -1226 0263
C 4335 -1248 0092
N 5010 -0212 -0396
C 4286 0860 -0720
C 2910 0902 -0560
H 2416 -2073 0664
H 4902 -2132 0361
H 4816 1716 -1121
H 2338 1779 -0827
n) AlI (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S18
o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S20
d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S22
f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S23
i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S10
Figure S8 Optimized structures and xyz coordinates for considered aluminum compounds
B3LYPTZVP level of theory
X Y Z
N -1377 0012 -0093
C -0683 1157 -0096
C 0702 1145 -0097
N 1377 -0011 -0093
C 0683 -1157 -0096
C -0702 -1145 -0097
H -1248 2080 -0108
H 1279 2060 -0113
H 1248 -2079 -0108
H -1278 -2060 -0112
Al 3437 -0001 0008
Cl 3710 0310 2094
Cl 3911 -1943 -0731
Cl 3895 1657 -1249
Al -3438 0001 0008
Cl -3895 -1654 -1252
Cl -3710 -0314 2093
Cl -3911 1945 -0727
X Y Z
N 3671 0002 -0002
C 2969 -1130 -0018
C 1582 -1142 -0050
N 0895 0011 -0063
C 1589 1159 -0050
C 2977 1138 -0019
H 3524 -2061 -0008
H 1009 -2059 -0075
H 1020 2079 -0074
H 3537 2065 -0009
Al -1131 0001 0002
Cl -1502 -0192 2095
Cl -1643 1895 -0845
Cl -1622 -1719 -1167
X Y Z
C -3663 0001 0000
C -2962 1200 -0018
C -1579 1169 -0053
N -0895 0010 -0067
C -1572 -1153 -0054
C -2954 -1194 -0019
H -3473 2153 -0008
H -0985 2072 -0077
H -0973 -2054 -0080
H -3458 -2150 -0010
H -4746 -0003 0026
Al 1113 0001 0002
Cl 1517 -0174 2095
Cl 1639 -1726 -1149
Cl 1656 1886 -0859
a) AlCl Py3middot
b) AlCl pyz3middot
c) AlCl pyz AlCl3 3middot middot
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S11
X Y Z
N -4969 0006 -0030
C -4247 0810 0750
C -2861 0771 0775
N -2181 -0091 0006
C -2896 -0902 -0781
C -4285 -0844 -0791
H -4786 1510 1378
H -2284 1423 1416
H -2345 -1599 -1396
H -4854 -1507 -1432
Al 0000 0000 0006
Cl 0000 0000 2193
Cl 0164 -1897 -1071
Cl -0164 1897 -1071
N 2181 0091 0007
C 2896 0902 -0781
C 4285 0844 -0791
N 4969 -0006 -0030
C 4247 -0810 0750C 2861 -0771 0775
H 2345 1599 -1396
H 4854 1507 -1432
H 4786 -1511 1378
H 2284 -1423 1416
d) AlCl (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S12
X Y Z
N 0000 -1390 0313
C 0000 -0695 1451
C 0000 0695 1451
N 0000 1390 0313
C 0000 0691 -0830
C 0000 -0691 -0830
H 0000 -1258 2374
H 0000 1258 2374
H 0000 1249 -1755
H 0000 -1249 -1755
Al 0000 3614 0169
Cl 1880 3466 -0928
Cl -1880 3466 -0928
Cl 0000 3798 2342
Al 0000 -3614 0169
Cl -1880 -3466 -0928
Cl 1880 -3466 -0928
Cl 0000 -3798 2342
N 0000 -5757 -0124C 0000 -6214 -1385
C 0000 -7574 -1652N 0000 -8490 -0683
C 0000 -8029 0564C 0000 -6669 0855
H 0000 -5480 -2178H 0000 -7932 -2675
H 0000 -8758 1365
H 0000 -6298 1870N 0000 5757 -0124
C 0000 6669 0855C 0000 8029 0564
N 0000 8490 -0683C 0000 7574 -1652
C 0000 6214 -1385H 0000 6298 1870
H 0000 8758 1365H 0000 7932 -2675
H 0000 5480 -2178
e) (AlCl ) (pyz)3 2 3
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S13
X Y Z
N -1379 0020 -0102
C -0677 1160 -0103
C 0709 1140 -0105
N 1379 -0020 -0102
C 0677 -1160 -0103
C -0709 -1140 -0105
H -1235 2087 -0110
H 1287 2053 -0119
H 1235 -2087 -0110
H -1287 -2053 -0119
Al 3450 0002 -0008
Br 3740 0589 2188
Br 4004 -2153 -0570
Br 3945 1626 -1551
Al -3450 -0002 -0008
Br -3945 -1626 -1551
Br -3740 -0589 2188
Br -4004 2154 -0570
X Y Z
C -4242 0080 -0114
C -3526 1271 -0114
C -2143 1223 -0113
N -1471 0057 -0111
C -2164 -1098 -0113
C -3546 -1123 -0113
H -4026 2230 -0117
H -1539 2120 -0119
H -1577 -2007 -0122
H -4062 -2074 -0116
H -5325 0089 -0116
Al 0541 -0001 0004
Br 0905 -0462 2232
Br 1115 -1718 -1426
Br 1224 2097 -0672
f) AlBr Py3middot
g) AlBr pyz3middot
h) AlBr pyz AlBr3 3middot middot
X Y Z
N 4244 0081 -0125
C 3556 -1060 -0119
C 2169 -1090 -0114
N 1466 0054 -0112
C 2146 1211 -0119
C 3534 1208 -0125
H 4123 -1983 -0121
H 1610 -2016 -0119
H 1565 2123 -0126
H 4082 2142 -0132
Al -0567 -0003 0007
Br -0887 -0431 2243
Br -1216 2091 -0699
Br -1109 -1740 -1402
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S14
X Y Z
N -4996 -0097 0013
C -4277 0761 0737
C -2890 0750 0739
N -2204 -0137 0005
C -2917 -1000 -0728
C -4307 -0970 -0716
H -4819 1482 1338
H -2320 1449 1334
H -2364 -1716 -1319
H -4872 -1676 -1314
Al 0000 0000 -0012
Br 0000 0000 2348
Br 0243 -2033 -1182
Br -0243 2033 -1182
N 2204 0137 0005
C 2917 1000 -0728
C 4307 0970 -0716
N 4996 0097 0013
C 4277 -0761 0737C 2890 -0750 0739
H 2364 1716 -1319H 4872 1676 -1314
H 4819 -1482 1338H 2320 -1449 1334
i) AlBr (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S15
X Y Z
N -1391 0048 -0040
C -0646 0600 -1003
C 0739 0552 -0962
N 1391 -0048 0040
C 0646 -0600 1003
C -0739 -0552 0962
H -1169 1088 -1813
H 1332 0999 -1747
H 1169 -1087 1813
H -1332 -0999 1747
Al 3649 0031 0042
Br 3785 -1446 1868
Br 3615 -0823 -2153
Br 3424 2342 0420
Al -3649 -0031 -0042
Br -3424 -2342 -0421
Br -3615 0822 2153
Br -3785 1446 -1867
N -5829 -0094 0032
C -6572 -1191 -0152
C -7961 -1130 -0096
N -8617 0003 0138
C -7867 1090 0320
C -6482 1054 0269
H -6046 -2115 -0341
H -8551 -2026 -0247
H -8382 2024 0513
H -5887 1943 0421
N 5829 0094 -0032
C 6572 1191 0151
C 7961 1130 0096
N 8617 -0003 -0138
C 7867 -1091 -0320
C 6482 -1054 -0269
H 6046 2115 0341
H 8552 2026 0247
H 8382 -2024 -0513
H 5887 -1943 -0420
j) (AlBr ) (pyz)3 2 3
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S16
X Y Z
N 1382 -0013 -0121
C 0682 -1156 -0119
C -0703 -1142 -0120
N -1382 0013 -0121
C -0682 1156 -0119
C 0703 1142 -0120
H 1241 -2082 -0128
H -1277 -2059 -0134
H -1241 2082 -0128
H 1277 2059 -0134
Al -3470 -0006 -0020
I -3767 -0416 2451
I -4124 2286 -0857
I -4054 -1937 -1541
Al 3470 0006 -0020
I 4054 1937 -1541
I 3767 0416 2451
I 4124 -2286 -0857
X Y Z
N -1808 -0040 0000
Al 0220 0038 0000
I 0828 -1193 2134
I 0828 2503 0000
I 0828 -1193 -2134
C -4570 -0274 0000
C -2392 -1255 0000
C -2585 1057 0000
C -3967 0977 0000
C -3765 -1408 0000
H -1727 -2108 0000
H -2066 2007 0000
H -4553 1886 0000
H -4189 -2403 0000
H -5649 -0366 0000
X Y Z
N -4439 0000 -1124
C -3756 1133 -0975
C -2400 1149 -0679
N -1722 0000 -0532
C -2400 -1149 -0679
C -3756 -1133 -0975
H -4299 2063 -1094
H -1843 2070 -0567
H -1843 -2070 -0567
H -4299 -2063 -1094
Al 0249 0000 0041
I 0022 0000 2561
I 1178 -2136 -0957
I 1178 2136 -0957
k) AlI Py3middot
l) AlI pyz3middot
m) AlI pyz AlI3 3middot middot
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S17
X Y Z
N -5010 0212 -0396
C -4286 -0860 -0720
C -2910 -0902 -0560
N -2236 0146 -0063
C -2954 1226 0263
C -4335 1248 0092
H -4816 -1716 -1121
H -2338 -1779 -0827
H -2416 2073 0664
H -4902 2132 0361
Al 0000 0000 0059
I 0000 0000 -2545
I 0252 2176 1448
I -0252 -2176 1448
N 2236 -0146 -0063
C 2954 -1226 0263
C 4335 -1248 0092
N 5010 -0212 -0396
C 4286 0860 -0720
C 2910 0902 -0560
H 2416 -2073 0664
H 4902 -2132 0361
H 4816 1716 -1121
H 2338 1779 -0827
n) AlI (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S18
o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S20
d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S22
f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S23
i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S11
X Y Z
N -4969 0006 -0030
C -4247 0810 0750
C -2861 0771 0775
N -2181 -0091 0006
C -2896 -0902 -0781
C -4285 -0844 -0791
H -4786 1510 1378
H -2284 1423 1416
H -2345 -1599 -1396
H -4854 -1507 -1432
Al 0000 0000 0006
Cl 0000 0000 2193
Cl 0164 -1897 -1071
Cl -0164 1897 -1071
N 2181 0091 0007
C 2896 0902 -0781
C 4285 0844 -0791
N 4969 -0006 -0030
C 4247 -0810 0750C 2861 -0771 0775
H 2345 1599 -1396
H 4854 1507 -1432
H 4786 -1511 1378
H 2284 -1423 1416
d) AlCl (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S12
X Y Z
N 0000 -1390 0313
C 0000 -0695 1451
C 0000 0695 1451
N 0000 1390 0313
C 0000 0691 -0830
C 0000 -0691 -0830
H 0000 -1258 2374
H 0000 1258 2374
H 0000 1249 -1755
H 0000 -1249 -1755
Al 0000 3614 0169
Cl 1880 3466 -0928
Cl -1880 3466 -0928
Cl 0000 3798 2342
Al 0000 -3614 0169
Cl -1880 -3466 -0928
Cl 1880 -3466 -0928
Cl 0000 -3798 2342
N 0000 -5757 -0124C 0000 -6214 -1385
C 0000 -7574 -1652N 0000 -8490 -0683
C 0000 -8029 0564C 0000 -6669 0855
H 0000 -5480 -2178H 0000 -7932 -2675
H 0000 -8758 1365
H 0000 -6298 1870N 0000 5757 -0124
C 0000 6669 0855C 0000 8029 0564
N 0000 8490 -0683C 0000 7574 -1652
C 0000 6214 -1385H 0000 6298 1870
H 0000 8758 1365H 0000 7932 -2675
H 0000 5480 -2178
e) (AlCl ) (pyz)3 2 3
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S13
X Y Z
N -1379 0020 -0102
C -0677 1160 -0103
C 0709 1140 -0105
N 1379 -0020 -0102
C 0677 -1160 -0103
C -0709 -1140 -0105
H -1235 2087 -0110
H 1287 2053 -0119
H 1235 -2087 -0110
H -1287 -2053 -0119
Al 3450 0002 -0008
Br 3740 0589 2188
Br 4004 -2153 -0570
Br 3945 1626 -1551
Al -3450 -0002 -0008
Br -3945 -1626 -1551
Br -3740 -0589 2188
Br -4004 2154 -0570
X Y Z
C -4242 0080 -0114
C -3526 1271 -0114
C -2143 1223 -0113
N -1471 0057 -0111
C -2164 -1098 -0113
C -3546 -1123 -0113
H -4026 2230 -0117
H -1539 2120 -0119
H -1577 -2007 -0122
H -4062 -2074 -0116
H -5325 0089 -0116
Al 0541 -0001 0004
Br 0905 -0462 2232
Br 1115 -1718 -1426
Br 1224 2097 -0672
f) AlBr Py3middot
g) AlBr pyz3middot
h) AlBr pyz AlBr3 3middot middot
X Y Z
N 4244 0081 -0125
C 3556 -1060 -0119
C 2169 -1090 -0114
N 1466 0054 -0112
C 2146 1211 -0119
C 3534 1208 -0125
H 4123 -1983 -0121
H 1610 -2016 -0119
H 1565 2123 -0126
H 4082 2142 -0132
Al -0567 -0003 0007
Br -0887 -0431 2243
Br -1216 2091 -0699
Br -1109 -1740 -1402
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S14
X Y Z
N -4996 -0097 0013
C -4277 0761 0737
C -2890 0750 0739
N -2204 -0137 0005
C -2917 -1000 -0728
C -4307 -0970 -0716
H -4819 1482 1338
H -2320 1449 1334
H -2364 -1716 -1319
H -4872 -1676 -1314
Al 0000 0000 -0012
Br 0000 0000 2348
Br 0243 -2033 -1182
Br -0243 2033 -1182
N 2204 0137 0005
C 2917 1000 -0728
C 4307 0970 -0716
N 4996 0097 0013
C 4277 -0761 0737C 2890 -0750 0739
H 2364 1716 -1319H 4872 1676 -1314
H 4819 -1482 1338H 2320 -1449 1334
i) AlBr (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S15
X Y Z
N -1391 0048 -0040
C -0646 0600 -1003
C 0739 0552 -0962
N 1391 -0048 0040
C 0646 -0600 1003
C -0739 -0552 0962
H -1169 1088 -1813
H 1332 0999 -1747
H 1169 -1087 1813
H -1332 -0999 1747
Al 3649 0031 0042
Br 3785 -1446 1868
Br 3615 -0823 -2153
Br 3424 2342 0420
Al -3649 -0031 -0042
Br -3424 -2342 -0421
Br -3615 0822 2153
Br -3785 1446 -1867
N -5829 -0094 0032
C -6572 -1191 -0152
C -7961 -1130 -0096
N -8617 0003 0138
C -7867 1090 0320
C -6482 1054 0269
H -6046 -2115 -0341
H -8551 -2026 -0247
H -8382 2024 0513
H -5887 1943 0421
N 5829 0094 -0032
C 6572 1191 0151
C 7961 1130 0096
N 8617 -0003 -0138
C 7867 -1091 -0320
C 6482 -1054 -0269
H 6046 2115 0341
H 8552 2026 0247
H 8382 -2024 -0513
H 5887 -1943 -0420
j) (AlBr ) (pyz)3 2 3
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S16
X Y Z
N 1382 -0013 -0121
C 0682 -1156 -0119
C -0703 -1142 -0120
N -1382 0013 -0121
C -0682 1156 -0119
C 0703 1142 -0120
H 1241 -2082 -0128
H -1277 -2059 -0134
H -1241 2082 -0128
H 1277 2059 -0134
Al -3470 -0006 -0020
I -3767 -0416 2451
I -4124 2286 -0857
I -4054 -1937 -1541
Al 3470 0006 -0020
I 4054 1937 -1541
I 3767 0416 2451
I 4124 -2286 -0857
X Y Z
N -1808 -0040 0000
Al 0220 0038 0000
I 0828 -1193 2134
I 0828 2503 0000
I 0828 -1193 -2134
C -4570 -0274 0000
C -2392 -1255 0000
C -2585 1057 0000
C -3967 0977 0000
C -3765 -1408 0000
H -1727 -2108 0000
H -2066 2007 0000
H -4553 1886 0000
H -4189 -2403 0000
H -5649 -0366 0000
X Y Z
N -4439 0000 -1124
C -3756 1133 -0975
C -2400 1149 -0679
N -1722 0000 -0532
C -2400 -1149 -0679
C -3756 -1133 -0975
H -4299 2063 -1094
H -1843 2070 -0567
H -1843 -2070 -0567
H -4299 -2063 -1094
Al 0249 0000 0041
I 0022 0000 2561
I 1178 -2136 -0957
I 1178 2136 -0957
k) AlI Py3middot
l) AlI pyz3middot
m) AlI pyz AlI3 3middot middot
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S17
X Y Z
N -5010 0212 -0396
C -4286 -0860 -0720
C -2910 -0902 -0560
N -2236 0146 -0063
C -2954 1226 0263
C -4335 1248 0092
H -4816 -1716 -1121
H -2338 -1779 -0827
H -2416 2073 0664
H -4902 2132 0361
Al 0000 0000 0059
I 0000 0000 -2545
I 0252 2176 1448
I -0252 -2176 1448
N 2236 -0146 -0063
C 2954 -1226 0263
C 4335 -1248 0092
N 5010 -0212 -0396
C 4286 0860 -0720
C 2910 0902 -0560
H 2416 -2073 0664
H 4902 -2132 0361
H 4816 1716 -1121
H 2338 1779 -0827
n) AlI (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S18
o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S20
d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S22
f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S23
i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S12
X Y Z
N 0000 -1390 0313
C 0000 -0695 1451
C 0000 0695 1451
N 0000 1390 0313
C 0000 0691 -0830
C 0000 -0691 -0830
H 0000 -1258 2374
H 0000 1258 2374
H 0000 1249 -1755
H 0000 -1249 -1755
Al 0000 3614 0169
Cl 1880 3466 -0928
Cl -1880 3466 -0928
Cl 0000 3798 2342
Al 0000 -3614 0169
Cl -1880 -3466 -0928
Cl 1880 -3466 -0928
Cl 0000 -3798 2342
N 0000 -5757 -0124C 0000 -6214 -1385
C 0000 -7574 -1652N 0000 -8490 -0683
C 0000 -8029 0564C 0000 -6669 0855
H 0000 -5480 -2178H 0000 -7932 -2675
H 0000 -8758 1365
H 0000 -6298 1870N 0000 5757 -0124
C 0000 6669 0855C 0000 8029 0564
N 0000 8490 -0683C 0000 7574 -1652
C 0000 6214 -1385H 0000 6298 1870
H 0000 8758 1365H 0000 7932 -2675
H 0000 5480 -2178
e) (AlCl ) (pyz)3 2 3
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S13
X Y Z
N -1379 0020 -0102
C -0677 1160 -0103
C 0709 1140 -0105
N 1379 -0020 -0102
C 0677 -1160 -0103
C -0709 -1140 -0105
H -1235 2087 -0110
H 1287 2053 -0119
H 1235 -2087 -0110
H -1287 -2053 -0119
Al 3450 0002 -0008
Br 3740 0589 2188
Br 4004 -2153 -0570
Br 3945 1626 -1551
Al -3450 -0002 -0008
Br -3945 -1626 -1551
Br -3740 -0589 2188
Br -4004 2154 -0570
X Y Z
C -4242 0080 -0114
C -3526 1271 -0114
C -2143 1223 -0113
N -1471 0057 -0111
C -2164 -1098 -0113
C -3546 -1123 -0113
H -4026 2230 -0117
H -1539 2120 -0119
H -1577 -2007 -0122
H -4062 -2074 -0116
H -5325 0089 -0116
Al 0541 -0001 0004
Br 0905 -0462 2232
Br 1115 -1718 -1426
Br 1224 2097 -0672
f) AlBr Py3middot
g) AlBr pyz3middot
h) AlBr pyz AlBr3 3middot middot
X Y Z
N 4244 0081 -0125
C 3556 -1060 -0119
C 2169 -1090 -0114
N 1466 0054 -0112
C 2146 1211 -0119
C 3534 1208 -0125
H 4123 -1983 -0121
H 1610 -2016 -0119
H 1565 2123 -0126
H 4082 2142 -0132
Al -0567 -0003 0007
Br -0887 -0431 2243
Br -1216 2091 -0699
Br -1109 -1740 -1402
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S14
X Y Z
N -4996 -0097 0013
C -4277 0761 0737
C -2890 0750 0739
N -2204 -0137 0005
C -2917 -1000 -0728
C -4307 -0970 -0716
H -4819 1482 1338
H -2320 1449 1334
H -2364 -1716 -1319
H -4872 -1676 -1314
Al 0000 0000 -0012
Br 0000 0000 2348
Br 0243 -2033 -1182
Br -0243 2033 -1182
N 2204 0137 0005
C 2917 1000 -0728
C 4307 0970 -0716
N 4996 0097 0013
C 4277 -0761 0737C 2890 -0750 0739
H 2364 1716 -1319H 4872 1676 -1314
H 4819 -1482 1338H 2320 -1449 1334
i) AlBr (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S15
X Y Z
N -1391 0048 -0040
C -0646 0600 -1003
C 0739 0552 -0962
N 1391 -0048 0040
C 0646 -0600 1003
C -0739 -0552 0962
H -1169 1088 -1813
H 1332 0999 -1747
H 1169 -1087 1813
H -1332 -0999 1747
Al 3649 0031 0042
Br 3785 -1446 1868
Br 3615 -0823 -2153
Br 3424 2342 0420
Al -3649 -0031 -0042
Br -3424 -2342 -0421
Br -3615 0822 2153
Br -3785 1446 -1867
N -5829 -0094 0032
C -6572 -1191 -0152
C -7961 -1130 -0096
N -8617 0003 0138
C -7867 1090 0320
C -6482 1054 0269
H -6046 -2115 -0341
H -8551 -2026 -0247
H -8382 2024 0513
H -5887 1943 0421
N 5829 0094 -0032
C 6572 1191 0151
C 7961 1130 0096
N 8617 -0003 -0138
C 7867 -1091 -0320
C 6482 -1054 -0269
H 6046 2115 0341
H 8552 2026 0247
H 8382 -2024 -0513
H 5887 -1943 -0420
j) (AlBr ) (pyz)3 2 3
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S16
X Y Z
N 1382 -0013 -0121
C 0682 -1156 -0119
C -0703 -1142 -0120
N -1382 0013 -0121
C -0682 1156 -0119
C 0703 1142 -0120
H 1241 -2082 -0128
H -1277 -2059 -0134
H -1241 2082 -0128
H 1277 2059 -0134
Al -3470 -0006 -0020
I -3767 -0416 2451
I -4124 2286 -0857
I -4054 -1937 -1541
Al 3470 0006 -0020
I 4054 1937 -1541
I 3767 0416 2451
I 4124 -2286 -0857
X Y Z
N -1808 -0040 0000
Al 0220 0038 0000
I 0828 -1193 2134
I 0828 2503 0000
I 0828 -1193 -2134
C -4570 -0274 0000
C -2392 -1255 0000
C -2585 1057 0000
C -3967 0977 0000
C -3765 -1408 0000
H -1727 -2108 0000
H -2066 2007 0000
H -4553 1886 0000
H -4189 -2403 0000
H -5649 -0366 0000
X Y Z
N -4439 0000 -1124
C -3756 1133 -0975
C -2400 1149 -0679
N -1722 0000 -0532
C -2400 -1149 -0679
C -3756 -1133 -0975
H -4299 2063 -1094
H -1843 2070 -0567
H -1843 -2070 -0567
H -4299 -2063 -1094
Al 0249 0000 0041
I 0022 0000 2561
I 1178 -2136 -0957
I 1178 2136 -0957
k) AlI Py3middot
l) AlI pyz3middot
m) AlI pyz AlI3 3middot middot
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S17
X Y Z
N -5010 0212 -0396
C -4286 -0860 -0720
C -2910 -0902 -0560
N -2236 0146 -0063
C -2954 1226 0263
C -4335 1248 0092
H -4816 -1716 -1121
H -2338 -1779 -0827
H -2416 2073 0664
H -4902 2132 0361
Al 0000 0000 0059
I 0000 0000 -2545
I 0252 2176 1448
I -0252 -2176 1448
N 2236 -0146 -0063
C 2954 -1226 0263
C 4335 -1248 0092
N 5010 -0212 -0396
C 4286 0860 -0720
C 2910 0902 -0560
H 2416 -2073 0664
H 4902 -2132 0361
H 4816 1716 -1121
H 2338 1779 -0827
n) AlI (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S18
o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S20
d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S22
f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S23
i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S13
X Y Z
N -1379 0020 -0102
C -0677 1160 -0103
C 0709 1140 -0105
N 1379 -0020 -0102
C 0677 -1160 -0103
C -0709 -1140 -0105
H -1235 2087 -0110
H 1287 2053 -0119
H 1235 -2087 -0110
H -1287 -2053 -0119
Al 3450 0002 -0008
Br 3740 0589 2188
Br 4004 -2153 -0570
Br 3945 1626 -1551
Al -3450 -0002 -0008
Br -3945 -1626 -1551
Br -3740 -0589 2188
Br -4004 2154 -0570
X Y Z
C -4242 0080 -0114
C -3526 1271 -0114
C -2143 1223 -0113
N -1471 0057 -0111
C -2164 -1098 -0113
C -3546 -1123 -0113
H -4026 2230 -0117
H -1539 2120 -0119
H -1577 -2007 -0122
H -4062 -2074 -0116
H -5325 0089 -0116
Al 0541 -0001 0004
Br 0905 -0462 2232
Br 1115 -1718 -1426
Br 1224 2097 -0672
f) AlBr Py3middot
g) AlBr pyz3middot
h) AlBr pyz AlBr3 3middot middot
X Y Z
N 4244 0081 -0125
C 3556 -1060 -0119
C 2169 -1090 -0114
N 1466 0054 -0112
C 2146 1211 -0119
C 3534 1208 -0125
H 4123 -1983 -0121
H 1610 -2016 -0119
H 1565 2123 -0126
H 4082 2142 -0132
Al -0567 -0003 0007
Br -0887 -0431 2243
Br -1216 2091 -0699
Br -1109 -1740 -1402
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S14
X Y Z
N -4996 -0097 0013
C -4277 0761 0737
C -2890 0750 0739
N -2204 -0137 0005
C -2917 -1000 -0728
C -4307 -0970 -0716
H -4819 1482 1338
H -2320 1449 1334
H -2364 -1716 -1319
H -4872 -1676 -1314
Al 0000 0000 -0012
Br 0000 0000 2348
Br 0243 -2033 -1182
Br -0243 2033 -1182
N 2204 0137 0005
C 2917 1000 -0728
C 4307 0970 -0716
N 4996 0097 0013
C 4277 -0761 0737C 2890 -0750 0739
H 2364 1716 -1319H 4872 1676 -1314
H 4819 -1482 1338H 2320 -1449 1334
i) AlBr (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S15
X Y Z
N -1391 0048 -0040
C -0646 0600 -1003
C 0739 0552 -0962
N 1391 -0048 0040
C 0646 -0600 1003
C -0739 -0552 0962
H -1169 1088 -1813
H 1332 0999 -1747
H 1169 -1087 1813
H -1332 -0999 1747
Al 3649 0031 0042
Br 3785 -1446 1868
Br 3615 -0823 -2153
Br 3424 2342 0420
Al -3649 -0031 -0042
Br -3424 -2342 -0421
Br -3615 0822 2153
Br -3785 1446 -1867
N -5829 -0094 0032
C -6572 -1191 -0152
C -7961 -1130 -0096
N -8617 0003 0138
C -7867 1090 0320
C -6482 1054 0269
H -6046 -2115 -0341
H -8551 -2026 -0247
H -8382 2024 0513
H -5887 1943 0421
N 5829 0094 -0032
C 6572 1191 0151
C 7961 1130 0096
N 8617 -0003 -0138
C 7867 -1091 -0320
C 6482 -1054 -0269
H 6046 2115 0341
H 8552 2026 0247
H 8382 -2024 -0513
H 5887 -1943 -0420
j) (AlBr ) (pyz)3 2 3
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S16
X Y Z
N 1382 -0013 -0121
C 0682 -1156 -0119
C -0703 -1142 -0120
N -1382 0013 -0121
C -0682 1156 -0119
C 0703 1142 -0120
H 1241 -2082 -0128
H -1277 -2059 -0134
H -1241 2082 -0128
H 1277 2059 -0134
Al -3470 -0006 -0020
I -3767 -0416 2451
I -4124 2286 -0857
I -4054 -1937 -1541
Al 3470 0006 -0020
I 4054 1937 -1541
I 3767 0416 2451
I 4124 -2286 -0857
X Y Z
N -1808 -0040 0000
Al 0220 0038 0000
I 0828 -1193 2134
I 0828 2503 0000
I 0828 -1193 -2134
C -4570 -0274 0000
C -2392 -1255 0000
C -2585 1057 0000
C -3967 0977 0000
C -3765 -1408 0000
H -1727 -2108 0000
H -2066 2007 0000
H -4553 1886 0000
H -4189 -2403 0000
H -5649 -0366 0000
X Y Z
N -4439 0000 -1124
C -3756 1133 -0975
C -2400 1149 -0679
N -1722 0000 -0532
C -2400 -1149 -0679
C -3756 -1133 -0975
H -4299 2063 -1094
H -1843 2070 -0567
H -1843 -2070 -0567
H -4299 -2063 -1094
Al 0249 0000 0041
I 0022 0000 2561
I 1178 -2136 -0957
I 1178 2136 -0957
k) AlI Py3middot
l) AlI pyz3middot
m) AlI pyz AlI3 3middot middot
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S17
X Y Z
N -5010 0212 -0396
C -4286 -0860 -0720
C -2910 -0902 -0560
N -2236 0146 -0063
C -2954 1226 0263
C -4335 1248 0092
H -4816 -1716 -1121
H -2338 -1779 -0827
H -2416 2073 0664
H -4902 2132 0361
Al 0000 0000 0059
I 0000 0000 -2545
I 0252 2176 1448
I -0252 -2176 1448
N 2236 -0146 -0063
C 2954 -1226 0263
C 4335 -1248 0092
N 5010 -0212 -0396
C 4286 0860 -0720
C 2910 0902 -0560
H 2416 -2073 0664
H 4902 -2132 0361
H 4816 1716 -1121
H 2338 1779 -0827
n) AlI (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S18
o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S20
d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S22
f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S23
i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S14
X Y Z
N -4996 -0097 0013
C -4277 0761 0737
C -2890 0750 0739
N -2204 -0137 0005
C -2917 -1000 -0728
C -4307 -0970 -0716
H -4819 1482 1338
H -2320 1449 1334
H -2364 -1716 -1319
H -4872 -1676 -1314
Al 0000 0000 -0012
Br 0000 0000 2348
Br 0243 -2033 -1182
Br -0243 2033 -1182
N 2204 0137 0005
C 2917 1000 -0728
C 4307 0970 -0716
N 4996 0097 0013
C 4277 -0761 0737C 2890 -0750 0739
H 2364 1716 -1319H 4872 1676 -1314
H 4819 -1482 1338H 2320 -1449 1334
i) AlBr (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S15
X Y Z
N -1391 0048 -0040
C -0646 0600 -1003
C 0739 0552 -0962
N 1391 -0048 0040
C 0646 -0600 1003
C -0739 -0552 0962
H -1169 1088 -1813
H 1332 0999 -1747
H 1169 -1087 1813
H -1332 -0999 1747
Al 3649 0031 0042
Br 3785 -1446 1868
Br 3615 -0823 -2153
Br 3424 2342 0420
Al -3649 -0031 -0042
Br -3424 -2342 -0421
Br -3615 0822 2153
Br -3785 1446 -1867
N -5829 -0094 0032
C -6572 -1191 -0152
C -7961 -1130 -0096
N -8617 0003 0138
C -7867 1090 0320
C -6482 1054 0269
H -6046 -2115 -0341
H -8551 -2026 -0247
H -8382 2024 0513
H -5887 1943 0421
N 5829 0094 -0032
C 6572 1191 0151
C 7961 1130 0096
N 8617 -0003 -0138
C 7867 -1091 -0320
C 6482 -1054 -0269
H 6046 2115 0341
H 8552 2026 0247
H 8382 -2024 -0513
H 5887 -1943 -0420
j) (AlBr ) (pyz)3 2 3
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S16
X Y Z
N 1382 -0013 -0121
C 0682 -1156 -0119
C -0703 -1142 -0120
N -1382 0013 -0121
C -0682 1156 -0119
C 0703 1142 -0120
H 1241 -2082 -0128
H -1277 -2059 -0134
H -1241 2082 -0128
H 1277 2059 -0134
Al -3470 -0006 -0020
I -3767 -0416 2451
I -4124 2286 -0857
I -4054 -1937 -1541
Al 3470 0006 -0020
I 4054 1937 -1541
I 3767 0416 2451
I 4124 -2286 -0857
X Y Z
N -1808 -0040 0000
Al 0220 0038 0000
I 0828 -1193 2134
I 0828 2503 0000
I 0828 -1193 -2134
C -4570 -0274 0000
C -2392 -1255 0000
C -2585 1057 0000
C -3967 0977 0000
C -3765 -1408 0000
H -1727 -2108 0000
H -2066 2007 0000
H -4553 1886 0000
H -4189 -2403 0000
H -5649 -0366 0000
X Y Z
N -4439 0000 -1124
C -3756 1133 -0975
C -2400 1149 -0679
N -1722 0000 -0532
C -2400 -1149 -0679
C -3756 -1133 -0975
H -4299 2063 -1094
H -1843 2070 -0567
H -1843 -2070 -0567
H -4299 -2063 -1094
Al 0249 0000 0041
I 0022 0000 2561
I 1178 -2136 -0957
I 1178 2136 -0957
k) AlI Py3middot
l) AlI pyz3middot
m) AlI pyz AlI3 3middot middot
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S17
X Y Z
N -5010 0212 -0396
C -4286 -0860 -0720
C -2910 -0902 -0560
N -2236 0146 -0063
C -2954 1226 0263
C -4335 1248 0092
H -4816 -1716 -1121
H -2338 -1779 -0827
H -2416 2073 0664
H -4902 2132 0361
Al 0000 0000 0059
I 0000 0000 -2545
I 0252 2176 1448
I -0252 -2176 1448
N 2236 -0146 -0063
C 2954 -1226 0263
C 4335 -1248 0092
N 5010 -0212 -0396
C 4286 0860 -0720
C 2910 0902 -0560
H 2416 -2073 0664
H 4902 -2132 0361
H 4816 1716 -1121
H 2338 1779 -0827
n) AlI (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S18
o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S20
d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S22
f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S23
i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S15
X Y Z
N -1391 0048 -0040
C -0646 0600 -1003
C 0739 0552 -0962
N 1391 -0048 0040
C 0646 -0600 1003
C -0739 -0552 0962
H -1169 1088 -1813
H 1332 0999 -1747
H 1169 -1087 1813
H -1332 -0999 1747
Al 3649 0031 0042
Br 3785 -1446 1868
Br 3615 -0823 -2153
Br 3424 2342 0420
Al -3649 -0031 -0042
Br -3424 -2342 -0421
Br -3615 0822 2153
Br -3785 1446 -1867
N -5829 -0094 0032
C -6572 -1191 -0152
C -7961 -1130 -0096
N -8617 0003 0138
C -7867 1090 0320
C -6482 1054 0269
H -6046 -2115 -0341
H -8551 -2026 -0247
H -8382 2024 0513
H -5887 1943 0421
N 5829 0094 -0032
C 6572 1191 0151
C 7961 1130 0096
N 8617 -0003 -0138
C 7867 -1091 -0320
C 6482 -1054 -0269
H 6046 2115 0341
H 8552 2026 0247
H 8382 -2024 -0513
H 5887 -1943 -0420
j) (AlBr ) (pyz)3 2 3
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S16
X Y Z
N 1382 -0013 -0121
C 0682 -1156 -0119
C -0703 -1142 -0120
N -1382 0013 -0121
C -0682 1156 -0119
C 0703 1142 -0120
H 1241 -2082 -0128
H -1277 -2059 -0134
H -1241 2082 -0128
H 1277 2059 -0134
Al -3470 -0006 -0020
I -3767 -0416 2451
I -4124 2286 -0857
I -4054 -1937 -1541
Al 3470 0006 -0020
I 4054 1937 -1541
I 3767 0416 2451
I 4124 -2286 -0857
X Y Z
N -1808 -0040 0000
Al 0220 0038 0000
I 0828 -1193 2134
I 0828 2503 0000
I 0828 -1193 -2134
C -4570 -0274 0000
C -2392 -1255 0000
C -2585 1057 0000
C -3967 0977 0000
C -3765 -1408 0000
H -1727 -2108 0000
H -2066 2007 0000
H -4553 1886 0000
H -4189 -2403 0000
H -5649 -0366 0000
X Y Z
N -4439 0000 -1124
C -3756 1133 -0975
C -2400 1149 -0679
N -1722 0000 -0532
C -2400 -1149 -0679
C -3756 -1133 -0975
H -4299 2063 -1094
H -1843 2070 -0567
H -1843 -2070 -0567
H -4299 -2063 -1094
Al 0249 0000 0041
I 0022 0000 2561
I 1178 -2136 -0957
I 1178 2136 -0957
k) AlI Py3middot
l) AlI pyz3middot
m) AlI pyz AlI3 3middot middot
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S17
X Y Z
N -5010 0212 -0396
C -4286 -0860 -0720
C -2910 -0902 -0560
N -2236 0146 -0063
C -2954 1226 0263
C -4335 1248 0092
H -4816 -1716 -1121
H -2338 -1779 -0827
H -2416 2073 0664
H -4902 2132 0361
Al 0000 0000 0059
I 0000 0000 -2545
I 0252 2176 1448
I -0252 -2176 1448
N 2236 -0146 -0063
C 2954 -1226 0263
C 4335 -1248 0092
N 5010 -0212 -0396
C 4286 0860 -0720
C 2910 0902 -0560
H 2416 -2073 0664
H 4902 -2132 0361
H 4816 1716 -1121
H 2338 1779 -0827
n) AlI (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S18
o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S20
d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S22
f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S23
i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S16
X Y Z
N 1382 -0013 -0121
C 0682 -1156 -0119
C -0703 -1142 -0120
N -1382 0013 -0121
C -0682 1156 -0119
C 0703 1142 -0120
H 1241 -2082 -0128
H -1277 -2059 -0134
H -1241 2082 -0128
H 1277 2059 -0134
Al -3470 -0006 -0020
I -3767 -0416 2451
I -4124 2286 -0857
I -4054 -1937 -1541
Al 3470 0006 -0020
I 4054 1937 -1541
I 3767 0416 2451
I 4124 -2286 -0857
X Y Z
N -1808 -0040 0000
Al 0220 0038 0000
I 0828 -1193 2134
I 0828 2503 0000
I 0828 -1193 -2134
C -4570 -0274 0000
C -2392 -1255 0000
C -2585 1057 0000
C -3967 0977 0000
C -3765 -1408 0000
H -1727 -2108 0000
H -2066 2007 0000
H -4553 1886 0000
H -4189 -2403 0000
H -5649 -0366 0000
X Y Z
N -4439 0000 -1124
C -3756 1133 -0975
C -2400 1149 -0679
N -1722 0000 -0532
C -2400 -1149 -0679
C -3756 -1133 -0975
H -4299 2063 -1094
H -1843 2070 -0567
H -1843 -2070 -0567
H -4299 -2063 -1094
Al 0249 0000 0041
I 0022 0000 2561
I 1178 -2136 -0957
I 1178 2136 -0957
k) AlI Py3middot
l) AlI pyz3middot
m) AlI pyz AlI3 3middot middot
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S17
X Y Z
N -5010 0212 -0396
C -4286 -0860 -0720
C -2910 -0902 -0560
N -2236 0146 -0063
C -2954 1226 0263
C -4335 1248 0092
H -4816 -1716 -1121
H -2338 -1779 -0827
H -2416 2073 0664
H -4902 2132 0361
Al 0000 0000 0059
I 0000 0000 -2545
I 0252 2176 1448
I -0252 -2176 1448
N 2236 -0146 -0063
C 2954 -1226 0263
C 4335 -1248 0092
N 5010 -0212 -0396
C 4286 0860 -0720
C 2910 0902 -0560
H 2416 -2073 0664
H 4902 -2132 0361
H 4816 1716 -1121
H 2338 1779 -0827
n) AlI (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S18
o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S20
d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S22
f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S23
i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S17
X Y Z
N -5010 0212 -0396
C -4286 -0860 -0720
C -2910 -0902 -0560
N -2236 0146 -0063
C -2954 1226 0263
C -4335 1248 0092
H -4816 -1716 -1121
H -2338 -1779 -0827
H -2416 2073 0664
H -4902 2132 0361
Al 0000 0000 0059
I 0000 0000 -2545
I 0252 2176 1448
I -0252 -2176 1448
N 2236 -0146 -0063
C 2954 -1226 0263
C 4335 -1248 0092
N 5010 -0212 -0396
C 4286 0860 -0720
C 2910 0902 -0560
H 2416 -2073 0664
H 4902 -2132 0361
H 4816 1716 -1121
H 2338 1779 -0827
n) AlI (pyz)3 2
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S18
o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S20
d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S22
f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S23
i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S18
o) (AlI ) (pyz)3 2 3
X Y Z
I -3903 -0204 2588
Al -3710 -0048 0012
I -3578 -2283 -1285
I -3503 2245 -1181
N -5911 0140 -0143
N -1393 -0075 0063
N -8667 0571 -0300
C -6698 -0637 -0895
C -6506 1137 0530
C -7875 1342 0446
C -8069 -0412 -0967
H -6223 -1441 -1439
H -5877 1771 1138
H -8341 2150 0997
H -8694 -1050 -1581
N 1393 -0075 -0063
C -0643 -0075 1169
C -0743 -0073 -1105
C 0643 -0075 -1169
C 0743 -0073 1105
H -1159 -0078 2119
H -1334 -0071 -2009
H 1159 -0078 -2119
H 1334 -0071 2009
I 3578 -2283 1285
Al 3710 -0048 -0012
I 3903 -0204 -2588
I 3503 2246 1181
N 5911 0140 0143
N 8667 0571 0300
C 6698 -0637 0896
C 6506 1137 -0530
C 7875 1342 -0446
C 8069 -0412 0967
H 6223 -1441 1439
H 5877 1771 -1138
H 8341 2150 -0997
H 8694 -1050 1581
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S20
d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S22
f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S23
i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S19
Figure 3S Optimized structures and xyz coordinates for considered gallium compounds
B3LYPTZVP level of theory
X Y Z
N 1372 -0007 -0090
C 0688 -1155 -0093
C -0699 -1148 -0094
N -1372 0007 -0090
C -0688 1155 -0093
C 0699 1148 -0094
H 1258 -2075 -0107
H -1276 -2063 -0110
H -1258 2075 -0107
H 1276 2063 -0110
Ga -3511 0001 0006
Cl -3790 -0207 2151
Cl -3947 1955 -0850
Cl -3938 -1762 -1197
Ga 3511 -0001 0006
Cl 3938 1762 -1196
Cl 3790 0207 2151
Cl 3947 -1955 -0851
a) GaCl Py3middot
b) GaCl pyz3middot
c) GaCl pyz GaCl3 3middot middot
X Y Z
C -0090 3856 0000
C -0091 3151 -1198
C -0091 1767 -1161
N -0089 1093 0000
C -0091 1767 1161
C -0091 3151 1198
H -0094 3660 -2152
H -0103 1168 -2062
H -0103 1168 2062
H -0094 3660 2152
H -0091 4939 0000
Ga 0023 -0976 0000
Cl 2178 -1337 0000
Cl -0997 -1513 1860
Cl -0997 -1513 -1860
X Y Z
N 0000 3870 0000
C 0016 3173 1135
C 0046 1784 1151
N 0059 1100 0000
C 0046 1784 -1151
C 0016 3173 -1135
H 0006 3731 2063
H 0071 1211 2068
H 0071 1211 -2068
H 0006 3731 -2063
Ga -0001 -0995 0000
Cl -2148 -1373 0000
Cl 1036 -1470 -1862
Cl 1036 -1470 1862
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S20
d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S22
f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S23
i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S20
d) GaCl (pyz)3 2
X Y Z
N 5055 -0009 -0045
C 4342 -0785 0770
C 2954 -0744 0805
N 2274 0089 0010
C 2977 0872 -0812
C 4366 0815 -0831
H 4888 -1462 1417
H 2380 -1371 1473
H 2417 1546 -1446
H 4932 1454 -1500
Ga 0000 0000 0011
Cl 0000 0000 2235
Cl -0148 1927 -1086
Cl 0148 -1927 -1086
N -2274 -0089 0010
C -2977 -0872 -0812
C -4366 -0815 -0831
N -5055 0009 -0045
C -4342 0785 0770
C -2954 0744 0805
H -2417 -1546 -1446
H -4932 -1454 -1500
H -4888 1462 1417
H -2380 1371 1474
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S22
f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S23
i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S21
e) (GaCl ) (pyz)3 2 3
X Y Z
N 1382 0085 0000
C 0693 0041 -1142
C -0693 -0043 -1142
N -1382 -0085 0000
C -0693 -0041 1142
C 0693 0043 1142
H 1257 0085 -2063
H -1257 -0087 -2063
H -1257 -0085 2064
H 1257 0087 2064
Ga -3717 -0004 0000
Cl -3752 -1126 1914
Cl -3513 2204 -0001
Cl -3752 -1127 -1913
Ga 3717 0005 0000
Cl 3752 1127 1914
Cl 3513 -2204 0001
Cl 3752 1126 -1914
N 5959 -0072 0000
C 6670 -1203 0000
C 8060 -1164 -0001
N 8740 -0021 -0001
C 8018 1100 -0001
C 6630 1085 0000
H 6115 -2131 0000
H 8633 -2084 -0001
H 8558 2039 -0001
H 6050 1998 0000
N -5959 0071 0000
C -6630 -1086 0000
C -8018 -1100 0000
N -8740 0020 0000
C -8060 1164 -0001
C -6670 1202 -0001
H -6049 -1998 0001
H -8558 -2040 0001
H -8634 2084 -0001
H -6115 2131 -0001
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S22
f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S23
i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S22
f) Br Py3middotGa
g) GaBr pyz3middot
h) Ga GaBr pyz Br3 3middot middot
X Y Z
C -4333 0063 -0094
C -3621 1255 -0099
C -2237 1210 -0103
N -1568 0046 -0104
C -2251 -1111 -0102
C -3635 -1139 -0097
H -4123 2213 -0100
H -1631 2107 -0115
H -1661 -2017 -0114
H -4149 -2091 -0096
H -5416 0069 -0091
Ga 0515 0000 0002
Br 0882 -0422 2274
Br 1065 -1775 -1423
Br 1151 2132 -0732
X Y Z
N 4341 0063 -0098
C 3650 -1076 -0097
C 2262 -1101 -0100
N 1568 0044 -0103
C 2245 1199 -0105
C 3635 1192 -0103
H 4215 -2001 -0095
H 1699 -2025 -0110
H 1665 2112 -0117
H 4186 2125 -0106
Ga -0542 -0001 0004
Br -0869 -0408 2279
Br -1138 2131 -0745
Br -1053 -1786 -1415
X Y Z
N 1374 -0018 -0110
C 0679 -1159 -0111
C -0708 -1141 -0113
N -1374 0018 -0110
C -0679 1159 -0111
C 0708 1141 -0113
H 1241 -2084 -0119
H -1288 -2054 -0127
H -1241 2084 -0119
H 1288 2054 -0127
Ga -3533 0000 -0006
Br -3802 -0539 2241
Br -4043 2185 -0634
Br -4003 -1694 -1534
Ga 3533 0000 -0006
Br 4003 1694 -1534
Br 3802 0539 2241
Br 4043 -2185 -0634
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S23
i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S23
i) GaBr (pyz)3 2
X Y Z
N 5107 0077 -0024
C 4396 -0745 0748
C 3008 -0726 0769
N 2322 0132 0006
C 3023 0960 -0773
C 4414 0924 -0780
H 4945 -1442 1371
H 2439 -1393 1401
H 2461 1653 -1385
H 4975 1600 -1415
Ga 0000 0000 -0001
Br 0000 0000 2377
Br -0216 2054 -1178
Br 0216 -2054 -1178
N -2322 -0132 0006
C -3023 -0960 -0773
C -4414 -0924 -0780
N -5107 -0077 -0024
C -4396 0745 0748
C -3008 0726 0769
H -2461 -1653 -1385
H -4975 -1600 -1415
H -4945 1442 1371
H -2439 1393 1401
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S24
j) (GaBr ) (pyz)3 2 3
X Y Z
N -1385 -0082 -0004
C -0706 0124 1126
C 0680 0204 1130
N 1385 0082 0004
C 0706 -0124 -1126
C -0680 -0204 -1130
H -1276 0218 2040
H 1233 0376 2044
H 1276 -0218 -2040
H -1233 -0376 -2044
Ga 3800 -0016 0004
Br 3536 -2369 0112
Br 3820 1086 -2097
Br 3859 1277 1992
Ga -3800 0016 -0004
Br -3859 -1277 -1992
Br -3820 -1086 2097
Br -3536 2369 -0112
N -6075 0102 0007
C -6747 -1051 0091
C -8135 -1066 0092
N -8858 0051 0011
C -8178 1191 -0072
C -6787 1229 -0075
H -6169 -1962 0158
H -8674 -2004 0161
H -8750 2109 -0140
H -6236 2157 -0142
N 6075 -0102 -0007
C 6747 1051 -0091
C 8135 1066 -0092
N 8858 -0051 -0011
C 8178 -1191 0072
C 6787 -1229 0075
H 6169 1962 -0158
H 8674 2004 -0161
H 8750 -2109 0140
H 6236 -2157 0142
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S25
X Y Z
N 1377 0000 -0096
C 0693 -1148 -0090
C -0693 -1148 -0090
N -1377 0000 -0096
C -0693 1148 -0090
C 0693 1148 -0090
H 1263 -2069 -0104
H -1263 -2069 -0104
H -1263 2069 -0104
H 1263 2069 -0104
Ga -3569 0000 -0012
I -3879 0001 2510
I -4113 2168 -1234
I -4114 -2168 -1232
Ga 3569 0000 -0012
I 4114 2168 -1232
I 3879 -0001 2510
I 4113 -2168 -1234
k) I Py3middotGa
l) GaI pyz3middot
m) Ga GaI pyz I3 3middot middot
X Y Z
N -1868 -0038 0000
Ga 0242 0034 0000
I 0814 -1216 2156
I 0814 2527 0000
I 0814 -1216 -2156
C -4627 -0247 0000
C -2457 -1246 0000
C -2629 1066 0000
C -4013 0999 0000
C -3833 -1388 0000
H -1798 -2104 0000
H -2100 2011 0000
H -4591 1914 0000
H -4267 -2379 0000
H -5706 -0329 0000
X Y Z
N -4529 0000 -1004
C -3842 1134 -0875
C -2477 1148 -0621
N -1801 0000 -0495
C -2477 -1148 -0621
C -3842 -1134 -0875
H -4389 2063 -0979
H -1914 2068 -0525
H -1914 -2068 -0525
H -4389 -2063 -0979
Ga 0274 0000 0041
I 0092 0000 2585
I 1126 -2166 -1008
I 1126 2166 -1008
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
S26
n) GaI (pyz)3 2 X Y Z
N -5204 0257 -0049
C -4505 -0638 -0748
C -3116 -0665 -0736
N -2415 0216 -0016
C -3105 1115 0689
C -4497 1128 0666
H -5063 -1356 -1336
H -2560 -1395 -1309
H -2537 1829 1271
H -5047 1863 1242
Ga 0000 0000 0015
I 0000 0000 -2574
I 0325 2216 1308
I -0325 -2216 1308
N 2415 -0216 -0016
C 3105 -1115 0689
C 4497 -1128 0666
N 5204 -0257 -0049
C 4505 0638 -0748
C 3116 0665 -0736
H 2537 -1829 1271
H 5047 -1863 1242
H 5063 1356 -1336
H 2560 1394 -1310
Electronic Supplementary Material (ESI) for Dalton TransactionsThis journal is copy The Royal Society of Chemistry 2013
