Reactivity of 1,2,4,5-tetracarboxylatebenzene with...
Transcript of Reactivity of 1,2,4,5-tetracarboxylatebenzene with...
Reactivity of 1,2,4,5-tetracarboxylatebenzene with Cobalt(II) Matthias Zeller2, Andrew R. Chema1, Paul S. Szalay1*, Allen D. Hunter2 Paul S. Szalay
Assistant Professor, Department of Chemistry
Muskingum College
163 Stormont St.
New Concord, OH 43762
phone: (740) 826-8231
fax: (740) 826-8229
Reactivity of 1,2,4,5-tetracarboxylatebenzene with Cobalt(II) Matthias Zeller2, Andrew R. Chema1, Paul S. Szalay1*, Allen D. Hunter2
The reactivity of the tetraanionic ligand 1,2,4,5-tetracarboxylatebenzene with cobalt(II) is described.
Reactivity of 1,2,4,5-tetracarboxylatebenzene with Cobalt(II) Matthias Zeller2, Andrew R. Chema1, Paul S. Szalay1*, Allen D. Hunter2
1) Department of Chemistry, Muskingum College, 163 Stormont Street, New Concord, OH 43762 2) Department of Chemistry, Youngstown State University, One University Plaza, Youngstown, OH 44555-3663 Abstract
The complexes [Co(H2O)6][Co(BTCA)(H2O)4]•7.2H2O (1) and [Na2Co(H2O)4(µ-
H2O)2(µ-BTCA)] (2) (BTCA = 1,2,4,5-tetracarboxylatebenzene) have been synthesized
and characterized by single crystal X-ray diffraction. Compound (1) crystallizes in the
triclinic space group P -1 with a = 6.8591(9) Å, b = 9.9691(13) Å, c = 10.9231(11) Å, α =
93.021(2)°, β = 104.883(2)°, and γ = 103.702° with Z = 1. This compound exhibits a 1-
dimensional structure of two alternating layers. A chain of cobalt ions and BTCA
constitute one layer. Cobalt complex ions and solvent water molecules occupy the other.
Compound (2) crystallizes in the monoclinic space group C 2/m with a = 8.8647(6) Å, b
= 10.5247(7) Å, c = 21.2265(14) Å, and β = 92.525(2)°, with Z = 2. This compound
consists of a 3-dimensional network of cobalt and sodium ions linked by BTCA. The
sodium complex moiety is disordered around a center of inversion.
Keywords: X-ray Crystallography, Cobalt Complexes, O-ligands
Introduction
An especially active research area in recent years has involved the preparation of both
molecular and solid state metal-organic hybrid compounds through the metal ion directed
assembly of organic molecular building blocks. Distinct molecular entities have
increasingly been employed as building blocks in the solution assembly of new solid state
materials.1 This approach is better enabling researchers to exploit the relationship
between the structure of a compound and its properties.
Potential properties of specific interest include magnetism and electrical conductivity.2
The choice of rigid building blocks have also lead to the preparation of robust three
dimensional porous lattices that maintain structural integrity with the loss of solvent
and/or guest molecules.3 Materials of this type have attracted attention as candidates for
exploring selective sorption, host-guest chemistry, and catalytic properties.4 Polar
molecular building blocks have been used to prepare materials that display non-linear
optical properties.5 Tri- and tetracarboxylates as ligands bridging multiple metal ions
have proven to be excellent candidates for the synthesis of metal-organic hybrid
compounds,6 and several compounds involving transition metals and anions of BTCAH4
have been reported.7
One avenue of our present investigations involves the use of benzene-1,2,4,5-
tetracarboxylic acid (BTCAH4) and its fully deprotonated form 1,2,4,5-
tetracarboxylatebenzene (BTCA) as rigid building blocks in the synthesis of metal-
organic hybrid compounds. Herein we report the room temperature solution phase
synthesis of two compounds, one composed of Co(II) and BTCA and the other composed
of Na(I), Co(II), and BTCA.
Experimental
Materials
The starting materials benzene-1,2,4,5-tetracarboxylic acid (BTCAH4), KOH, and
NaOH were all purchased from Aldrich. The salt Co(ClO4)2•6H2O was purchased from
Strem Chemicals. All reagents were used as received without further purification.
Acetonitrile was dried over anhydrous CaSO4 and distilled prior to use. All water was
distilled prior to its use.
X-Ray Crystallography
Diffraction data of both compounds have been collected with a 'Bruker AXS SMART
APEX CCD' diffractometer. The data for (1) and (2) were collected at 298 K and 100 K,
respectively using monochromatographed Mo Kα radiation with omega scan technique.
The unit cell was determined using SAINT+ and the structure was solved by direct
methods and refined by full matrix least squares against F2 with all reflections using the
SHELXTL programs.8
The interstitial water molecules of O12, O13 and O14 of compound (1) have been
found to have a large freedom of movement and are only partially occupied. Their
anisotropic displacement parameters have been restrained to be isotropic within a
standard deviation of 0.04, and the site occupancies refined to 68, 24 and 92%,
respectively. The cobalt coordinated water molecules defined by O7, O8, and O9 were
disordered over two positions with a ratio of 87:13. The anisotropic displacement
parameters of the minor component oxygen atoms have been restrained to be equal to that
of its major component counterpart.
The positions of the hydrogen atoms on the interstitial water molecule of O13 could
not reliably be determined from the diffraction data and have been omitted. The
hydrogen atoms of the water molecules of O10, O11, O12, and O14 were all located from
the electron density map and refined using different types of riding models. The positions
of the hydrogen atoms attached to O14 were not refined at all and were set to ride on the
oxygen atom. The hydrogen-oxygen distances of O10, O11 and O12 were restrained to
0.9 Å with a standard deviation of 0.02 and the respective hydrogen-hydrogen distances
within the water molecules were restrained to be the same within a standard deviation of
0.02.
The hydrogen atoms of the disordered water molecules defined by O7, O8, and O9
were tentatively found in the density Fourier map, but were all eventually added in
calculated positions. For each water molecule the first hydrogen atom was added as an
ideal OH group with respect to the cobalt core using an “AFIX 83” command. For the
second hydrogen atoms the hydrogen-oxygen distances were set to be equal to the first
within a standard deviation of 0.02 for the major disordered component and 0.01 for the
minor component. The hydrogen-hydrogen distances within all six coordinated water
molecules were set to be equal with a standard deviation of 0.02.
All hydrogen atoms discussed thus far were set to have an isotropic displacement
parameter of 1.5 times that of the adjacent oxygen atom. All other hydrogen atoms were
located from the electron difference map and refined isotropically.
The sodium ion Na1 and the oxygen atoms O4, O6 and O7 in compound (2) are
forming a moiety disordered over two positions. The two components are symmetry
dependent and the second component is created by an inversion center near the sodium
atom at ¾, ¾, ½. Due to the proximity of the two sodium ions and significant overlap,
they had to be refined isotropically. All other nonhydrogen atoms were refined
anisotropically. The bond lengths of Na1 to the terminal water ligands of O4 and O6
were restrained to be the same as were the anisotropic displacement parameters for O4
and O6. The sodium carboxylate interactions of Na1, O3, and O7 were treated in the
same fashion. The geometries of the water molecules defined by O4, O5, and O6 were
restrained to be equivalent. Crystal data and experimental details for both compounds are
listed in Table 1.
Syntheses
The compound [Co(H2O)6][Co(BTCA)(H2O)4]•7.2H2O (1) was prepared using a thin
tube slow diffusion reaction. Solid BTCAH4 (10.0 mg, 0.039 mmol) was dissolved in 8
mL of deionized water containing 4.0 mL of 0.05 M KOH (0.2 mmol). Solid
Co(ClO4)2•6H2O (10.4 mg, 0.039 mmol) was dissolved in 8 mL of acetonitrile. The
BTCA containing solution was added to a thin glass tube, 4 mm ID. The Co(ClO4)2
solution was added slowly on top of the BTCA containing solution such that the solutions
remained layered. The tube was allowed to stand for a week during which time pale
yellow crystals appeared. These crystals were harvested and analyzed by single crystal
X-ray diffraction. Yield 0.009g (67.0%).
The compound [Na2Co(H2O)4(µ-H2O)2(µ-BTCA)] (2) was prepared as follows. Solid
Co(ClO4)2•6H2O (10.4 mg, 0.039 mmol) and BTCAH4 (10.0 mg, 0.039 mmol ) were
dissolved separately in 8 mL quantities of deionized water. These solutions were then
mixed in a test tube. A 5.0 mL volume of 0.05 M (0.25 mmol) NaOH was added to this
solution over a period of 1 hour. The resulting mixture was capped and allowed to stand
for two weeks during which time pale pink crystals appeared. These crystals were
harvested and analyzed by single crystal X-ray diffraction. Yield 0.012g (61.7%).
Results and Discussion
The molecule benzenetetracarboxylic acid (BTCAH4) has structural features that make
it desirable as a precursor in reactions with metal ions to prepare metal-organic hybrid
compounds. The molecule possesses four divergent carboxylic acid groups with the
potential to act as binding sites for metal ions. The ten carbon backbone of the molecule
is rigid due to its aromatic nature. The carboxylic acid groups can be selectively
deprotonated to form the 1-, 2-, and 4- anions though the later two are by far the most
common.9 This deprotonation greatly increases the Lewis basic character of the molecule
and the resulting salts have very high aqueous solubility. The compound BTCAH4 is
noteworthy as a ligand because the carboxylate anion has nine known coordination
modes with metal ions.9 This variety of coordination capabilities makes single crystal X-
ray structure determination an especially important characterization tool for compounds
containing the anions of BTCAH4.
Since the fully protonated BTCAH4 is a poor nucleophile the process of deprotonating
the carboxylic acid groups can be used to slow the rate of the eventual reaction between
BTCA and metal ions. Slowing reactions can, of course, enhance crystal growing
conditions. In the synthesis of (1), BTCAH4 was deprotonated prior to the introduction
of an acetonitrile solution of Co(II) ions. Deprotonation prior to metal ion introduction
should lead to a more rapid initial reaction because BTCA is a much stronger nucleophile
than BTCAH4, however, the solutions of BTCA and Co(II) were layered in a thin tube
slowing down the bulk reaction. In the preparation of (2), aqueous solutions of BTCAH4
and Co(II) ions were mixed and then a solution of NaOH was added to the mixture. The
gradual introduction of base into the BTCAH and Co(II) mixture in the preparation of (2)
served to slow the reaction in that synthesis.
The structure of compound (1) (Figures 1-3) as determined by single crystal X-ray
diffraction consists of alternating layers. One layer consists of 1-dimensional chains of
Co(II) ions linked by trans carboxylate groups of BTCA. The inner coordination sphere
of these cobalt ions consists of two axial oxygen atoms from the BTCA carboxylate
groups and four equatorial water molecules, with the cobalt atom itself residing on an
inversion center.
Octahedral [Co(H2O)6]+2 ions occupy the second layer, taking up about half of its
volume with the other half being filled by interstitial water molecules. The complex ions
are offset from the cobalt-BTCA chains in the layers above and below them. They reside
between the centers of the cobalt-BTCA chains in the adjacent layers (Figure 2). The
cobalt atom of the complex ions is located on an inversion center and the water ligands
are disordered over two positions with a ratio of 87:13.
The cobalt ions in the BTCA chains consist of a slightly distorted octahedron. The
unique bond angles range from 87.01(8)° (O1-Co1-O6) to 91.12(9)° (O2-Co1-O6). As
expected, the lengths of the cobalt-oxygen bonds for the interaction of cobalt with the
anionic BTCA (Co1-O1) with a distance of 2.0777(18) Ǻ is shorter than the distances
between the cobalt center and the neutral water molecules Co1-O2 and Co1-O6 with
respective distances of to 2.130(2) and 2.101(2) Ǻ.
Numerous hydrogen bonding interactions are found within the structure of (1), which
will be briefly described in the following paragraph. A detailed summary of all the
hydrogen bonding interactions is listed in Table 6, and a representation of the hydrogen
bonding network is shown in Figure 3. Two types of hydrogen bonding interactions can
be distinguished within the structure of compound (1). The first type consists of strong
interactions between the carboxylate groups of the BTCA and the aquo ligands
coordinated to Co1 and Co2. These highly directional hydrogen bonds are formed
between the oxygen atoms O3, O4, and O5 of BTCA and the oxygen atoms O2, O6, O7,
O8 and O9 of the cobalt ions. These interactions are in part direct hydrogen bonds
between these atoms and partially they are bridged by the interstitial water molecules of
O10 and O11. (See Figure 3). The second type consists of hydrogen bonds towards the
remaining interstitial water molecules of O12, O13 and O14, which seem to be much
weaker and less directional. These water molecules are only partially occupied and
exhibit a large degree of thermal motion, thus their role seems to be that of mere
spacefillers without any contribution towards the structural features of the molecular
assembly. Do you think we should include the figure currently labeled Figure 3 as
well as one of the two you have at the end of this file. There is a good deal of
hydrogen bonding in this compound and that might help people understand it or it
might be overkill? What do you think?
Let’s keep Fig 1 to Fig 3, but that is enough, I think
The structure of (2) (Figure 4 & 5 Let’s add another figure showing the Na-chains
without disorder, the title picture should easily do) as determined by single crystal X-ray
diffraction consists of a three dimensional network of Co(II) and Na(I) sites linked by
BTCA. All of the cobalt and sodium ion sites are octahedrally coordinated. Each
monoanionic carboxylate group of BTCA is bridging a Co(II) ion and a Na(I) ion.
Therefore each tetraanionic BTCA is connected to a total of four Co(II) ions and four
Na(I) ions. The inner coordination sphere of Co(II) consists of two axial water molecules
and four equatorial oxygen atoms from separate carboxylate groups of BTCA. The inner
coordination sphere of the sodium ions consists of two trans terminal water molecules,
two trans bridging water molecules, and two trans oxygen atoms from the carboxylate
groups of separate BTCA ligands. The µ-aquo ligands bridge nearest neighbor sodium
ions. The cobalt ions reside on two-fold rotation axes. Mirror planes bisect the water
molecules that bridge the sodium ions.
We should mention that the sodiums are forming infinite chains etc
The sodium atoms and the surrounding oxygen atoms O4, O6 and O7 are disordered
over two positions. The two components are symmetry dependent and the second
component is created by an inversion center at ¾, ¾, ½. The coordination geometry of
Na1 is a distorted octahedron. The O5-Na1-O3, O5-Na1-O4A, and O3A-Na1-O4 angles
are 92.84(4)°, 89.01(4)° and 99.91(6)° respectively. The bond lengths of the sodium ion
to the two trans terminal water molecules of O4 and O6 average 2.404(6) Ǻ. The bond
length of the two disorderd sodium ions to the bridging water molecule of O5 is
expectedly longer with lengths of 2.436(11) and 2.691(12) Ǻ to Na1 and Na1A
respectively. The bond lengths of the sodium ion to the two trans carboxylate oxygens of
BTCA ligands, O3 and O4, average 2.342(5) Ǻ.
The coordination geometry of Co1 is also a distorted octahedron. The O1-Co1-O2
bond angle is 86.21(4)°. The bond from the cobalt ion to the terminal water ligand (Co1-
O2) is as expected longer than that of the cobalt center to the oxygen of the anionic
BTCA ligand (Co1-O1) with distances of 2.125(16) and 2.100(12) Ǻ respectively.
Several types of hydrogen bonding interactions are found within the network structure
of (2), which will be briefly described in the following paragraph. A detailed summary
of all the hydrogen bonding interactions is listed in Table 11. The first type are hydrogen
bonds between water molecules and carboxylate oxygen atoms (O2-H2···O3a, O4-
H4B···O1c and O6-H6A···O3g). These interactions are bridging each sodium and cobalt
moieties. There are also hydrogen bonding interactions between water molecules
coordinated to nearest neighbor sodium ions (O4-H4A···O6d) and coordinated to sodium
on one side and cobalt on the other (O2-H2···O7b). The water molecules bridging the
sodium atoms are forming hydrogen bonds with both carboxylate groups (O5-H5A···O7
and O5-H5A···O7f) as well as water molecules coordinated to cobalt ions (O5-
H5B···O2e). All hydrogen bonds in compound (2) are highly directional and no weak
interactions as in compound (1) are found here.
Summary
Despite using equivalent amounts of the starting materials Co(ClO4)2•6H2O and
BTCAH4 in the preparation of (1) and (2) relatively minor changes in the reaction
conditions produced significantly different structural results. Compound (1) exhibits an
alternating layered structure of cobalt-BTCA chains and cobalt complex ions. In
contrast, compound (2) consists of a three dimensional network of BTCA ligands, cobalt
(II) ions, and sodium ions. The incorporation of sodium ions in (2), but not potassium
ions in (1) was likely influenced by the presence of a greater excess of base in the
synthesis of (2). Additionally, in the synthesis of (2) all three reagents were combined in
a test tube (with the NaOH being added dropwise to the Co(II) and BTCAH4 solution)
and allowed to react. In the synthesis of (1), deprotonation of the BTCAH4 took place
prior to the introduction of the Co(II), which was subsequently added via thin tube slow
diffusion.
Acknowledgements
MZ was supported by NSF grant 0111511, CLP by ACS PRF grant 37228-B3, JCW by
ACS PRF grant 37228-B3-SRF, and the diffractometer was funded by NSF grant
0087210, by Ohio Board of Regents grant CAP-491, and by YSU.
Supplementary Material
CCDC-XXXXXX and CCDC-XXXXXX contain the supplementary crystallographic
data for this paper. These data can be obtained free of charge at
www.ccdc.cam.uk/conts/retrieving.html [or from the Cambridge Crystallographic Data
Centre (CCDC), 12 Union Road, Cambridge CB2 1EZ, UK; fax: +44(0)1223-336033;
email: [email protected]]
References
1. (a) Day, P., Gillespie, R. Philos. Trans. R. Soc. London, Ser. A 1985, A314. (b) Cotton,
F. A.; Lin, C.; Murillo, C. A. Acc. Chem. Res. 2001, 34, 759. (c) Day, P. J. Chem. Soc.,
Dalton Trans. 2000, 3483. (d) Fujita, M., Ed. Molecular Self-Assembly, Organic versus
Inorganic Approaches. Struct. Bonding 2000, 96. (e) Lehn, J.-M. Supramolecular
Chemistry, Concepts and Perspectives; VCH: Weinheim, Germany, 1995. (f) Hosseini,
M. W. New J. Chem. 1998, 22, 87. (g) Sauvage, J.-P., Dietrich-Buchecker, C., Eds.
Molecular Catenanes, Rotaxanes and Knots: A Journey Through the World of Molecular
Topology; Wiley-VCH: Weinheim, Germany, 1999. (h) Leininger, S.; Olenyuk, B.;
Stang, P. J. Chem. ReV. 2000, 100, 853. (i) Beer, P. D., Ed. Transition Metals in
Supramlecular Chemistry; Kluwer: Dordrecht, The Netherlands, 1994. (j) Robson, R.;
Batten, S. R. Angew. Chem., Int. Ed. 1998, 37, 1460. (k) O’Hare, D., Bruce, D. W. Eds.
Inorganic Materials; Wiley: Chichester, U.K., 1992.
2. (a) Lacroix, P. G.; Clement, R.; Nakatani, K.; Zyss, J.; Ledoux, I. Science 1994, 263,
658. (b) Sato, O.; Iyoda, T.; Fujishima, A.; Hashimoto, K. Science 1996, 271, 49. (c)
Day, P., Underhill, A. E., Eds. Metal-Organic and Organic Molecular Magnets. Philos.
Trans. R. Soc. London 1999, 357. (d) Kahn, O., Ed. Magnetism: A Supramolecular
Function; Kluwer Academic: Dordrecht, The Netherlands, 1996. (e) Kahn, O. Acc. Chem.
Res. 2000, 33, 647. (f) Veciana, J., Rovira, C., Amabilino, D. B., Eds. Supramolecular
Engineering of Synthetic Metallic Materials,Conductors and Magnets; NATO ASI Series
C518; Kluwer Academic: Dordrecht, The Netherlands, 1998. (g) Itoh, K., Kinoshita, M.,
Eds. Molecular Magnetism, New Magnetic Materials; Gordon and Breach-Kodansha:
Tokyo, 2000. (h) Sugano, S., Kojima, N., Eds. Magnetooptics; Springer-Verlag: Berlin,
2000. (i) Benard, S.; Yu, P.; Audiere, J. P.; Riviere, E.; Clement, R.; Guilhem, J.;
Tchertanov, L.; Nakatani, K. J. Am. Chem. Soc. 2000, 122, 9444. (j) Lacroix, P. G. Eur.
J. Inorg. Chem. 2001, 339.
3. (a) G. B. Gardner, D.; Venkataraman, J.; Moore, S.; and Lee, S. Nature. 374,1995,
792. (b) Venkataraman, D.; Lee, S.; Moore, J. S.; Zheng, P; Hirsch, K. A.; Gardner, G.
B.; Covey, A. C.; Prentice, C. L. Chem Mater. 1996, 8, 2030. (c) Venkataraman, D.;
Gardner, G. B.; Lee, S.; Moore, J. S. J. Am. Chem. Soc. 1995, 117, 11600. Yaghi, O. M.;
Li, G.; Li, H. Nature, 1995, 378, 703. (d) Ward, M. D. Nature, 1995, 374, 764. (e)
Eddaoudi, M., Li, H., Yaghi, O. M. J. Am. Chem. Soc. 2000, 122(7), 1391-1397. (f)
Kim, J.; Chen, B.; Reineke, T. M.; Li, H.; Eddaoudi, M.; Moler, D. B.; O'Keeffe, M.;
Yaghi, O. M. J. Am. Chem. Soc. 2001, 123(34), 8239-8247. (f) Yaghi, O. M.; Li, H.;
Davis, C.; Richardson, D.; Groy, T. L. Acc. Chem. Res. 1998, 31(8), 474-484. (g)
Eddaoudi, M., Moler, D., Li, H., Chen, B., Reineke,T., O’Keffe, M. and Yahghi, O.M.
Acc. Chem. Res. 2001, 34, 319-330.
4. (a) Kawata, S.; Kitagawa, S.; Kumagai, H.; Kudo, C.; Kamesaki, H.; Ishiyama, T.;
Kondo, M.; Katada, M. Inorg. Chem. 1996, 35, 4449. (b) Lagaly, G. Appl. Clay Sci.
1999, 15, 1. (c) Barton, T. J.; Bull, L. M.; Klemperer, W. G.; Loy, D. A.; McEnaney, B.;
Misono, M.; Monson, P. A.; Pez, G.; Scherer, G. W.; Vartuli, J. C.; Yaghi, O. M. Chem.
Mater. 1999, 2633, 3. (d) Yaghi, O. M.; Li, H.; Davis, C.; Richardson, D.; Groy, T. L.
Acc. Chem.Res. 1998, 31, 474. (e) Kitagawa, S.; Kondo, M. Bull. Chem. Soc. Jpn. 1998,
71, 1739. (f) Kawata, S.; Kitagawa, S.; Kumagai, H.; Ishiyama, T.; Honda, K.; Tobita,
H.; Adachi, K.; Katada, M. Chem. Mater. 1998, 10, 3902. (g) Kepert, C. J.; Rosseinsky,
M. J. Chem. Commun. 1998, 31. (h) Kepert, C. J.; Hesek, D.; Beer, P. D.; Rosseinsky, M.
J. Angew. Chem., Int. Ed. 1998, 37, 3158. (i) O’Keeffe, M.; Eddaoudi, M.; Li, H.;
Reineke, T.; Yaghi, O. M. J. Solid State Chem. 2000, 152, 3. (j) Kepert, C. J.; Prior, T. J.;
Rosseinsky, M. J. J. Am. Chem. Soc. 2000, 122, 5158. (k) Kepert, C. J.; Prior, T. J.;
Rosseinsky, M. J. J. Solid State Chem. 2000, 152, 261.
5. (a) Lin, W.; Evans, O. R.; Xiong, R.-G.; Wang, Z. J. Am. Chem. Soc. 1998, 120,
13272. (b) Evans, O. R.; Xiong, R.-G.; Wang, Z.; Wong, G. K.; Lin, W. Angew, Chem.
Int. Ed. Engl.1999, 38, 536.
6. (a) Yaghi, O. M.; Li, H.; Groy, T. L. J. Am. Chem. Soc. 1996, 118, 9096. Molinier, M.;
Powell, A. K.; Winpenny, R. E. P.; Wood, P. T. Chem. Commun. 1996, 823. (b) Yaghi,
O. M.; Davis, C. E.; Li, G.; Li, H. J. Am. Chem. Soc. 1997, 119, 2861. (c) Michaelides,
A.; Skoulika, S.; Kirtsis, V.; Raotopoulou, C.; Terzis, A. J. Chem.Res. 1997, 204. (d)
Yaghi, O. M.; Jernigan, R.; Li, H.; Davis, C. E.; Groy, T. L. J. Chem. Soc., Dalton
Trans.1997, 2383. . (e) Platter, M. J.; Howie, R. A.; Roberts, A. J. Chem. Commun. 1997,
893. (f) Platter, M. J.; Roberts, A. J.; Marr, J.; Lachowski, E. E.; Howie, R. A. J. Chem.
Soc., Dalton Trans. 1998, 797. (g) Platter, M. J.; Foreman, M. R. S. J.; Coronado, E.;
Gomez-Garcia, C. J.; Slawin, A. M. Z. J. Chem. Soc., Dalton Trans 1999, 4209. (h)
Chui, S. S.-Y.; Lo, S. M.-F.; Charmant, J. P. H.; Orpen, A. G.; Williams, I. D. Science
1999, 283, 1148. (i) Guillou, N.; Livage, C.; Marrot, J.; Ferey, G. Acta Crystallogr. 2000,
C56, 1427. (j) Livage, C.; Guillou, N.; Marrot, J.; Ferey, G. Chem. Mater. 2001, 13,
4387. (k) Foreman, M. R. S. J.; Gelbrich, T.; Hursthouse, M. B.; Platter, M. J. Inorg.
Chem. Commun. 2000, 3, 234. (l) Kumagai, H.; Akita-Tanaka, M.; Inoue, K.; Kurmoo,
M. J. Mater.Chem. 2001, 11, 2146. (m) Chu, D.-Q.; Xu, J.-Q.; Duan, L.-M.; Wang, T.-
G.; Tang, A.-Q.; Ye, L. Eur. J. Inorg. Chem. 2001, 1135.
7. (a) Usubaliev, B. T.; Shnulin, A. N.; Mamadov, H. S. Koord. Khim. 1983,8, 1532. (b)
Ward, D. L.; Luehrs, D. C. Acta Crystallogr. 1983, C39, 1370. (c) Robl, C.; Hentechel, S.
Mater. Res. Bull. 1991, 26, 1355. (d) Robl, C. Mater. Res. Bull. 1992, 27, 99. (e) Robl, C.
Z. Anorg. Allg. Chem. 1987, 554, 79. (f) Robl, C. Z. Naturforsch., B 1988, B43, 993. (g)
Poleti, D.; Stojakovic, D. R.; Prelesnik, B. V.; Herak, R. M. Acta Crystallogr. 1988, C44,
242. (h) Chaudhuri, P.; Oder, K.; Weighardt, K.; Gehring, S.; Haase, W.; Nuber, B. J.
Am. Chem. Soc. 1988, 100, 3657. (i) Poleti, D.; Karanovic, Lj. Acta Crystallogr. 1989,
C45, 1716. (31) (j) Chen, W.; Tioh, N. H.; Zou, J.-Z.; Xu, Z.; You, X. Z. Acta
Crystallogr. 1996, C52, 43. (k) Zou, J.-Z.; Liu, Q.; Xu, Z.; You, X. Z.; Huang, X.-Y.
Polyhedron 1998, 17, 1863. (l) Karanovic, L.; Poleti, D.; Bogdanovic, G. A.; Spasojevic-
de Bire, A. Acta Crystallogr. 1999, C55, 911. (m) Li, Y.-T.; Yan, C.-W.; Kong, X.-H.
Pol. J. Chem. 1999, 73(10), 1665. (n) Rochon, F. D.; Massarweh, G. Inorg. Chim. Acta
2000, 304, 190. (o) Cheng, D.; Zheng, Y.; Li, J.; Xu, D.; Xu, Y. Acta Crystallogr. 2000,
C56, 523. (p) Li, Y.-T.; Yan, C.-W, Synth. React. Inorg. Met.-Org. Chem. 2000, 30(6),
1069. (q) Yan, C.-W.; Li, Y.-T.; Liao, D.-Z. Chin. J. Chem. 2000, 18(3), 351. (r)
Gutschke, S. O. H.; Price, D. J.; Powell, A. K.; Wood, P. T. Eur. J. Inorg. Chem. 2001,
2739. (s) Chu, D.-Q.; Xu, J.-Q.; Duan, L.-M.; Wang, T.-G.; Tang, A.-Q.; Ye, L. Eur. J.
Inorg. Chem. 2001, 1135. (t) Kumagai, H.; Kepert, C. J.; and Kurmoo, M. Inorg. Chem.
2002, 41, 3410.
8. Bruker (1997). SAINT (Version 6.02), SMART for WNT/2000 (Version 5.625) and
SHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.
9. Kumagai, H.; Kepert, C. J.; and Kurmoo, M. Inorg. Chem. 2002, 41, 3410.
Table 1. X-ray crystal data and details of data collections and structure refinements. Compound (1) (2) CCDC deposit no. CCDC XXXXX CCDC XXXXX Color/shape yellow/plate pink/needle Formula C10H36.44Co2O25.70 C10H18CoNa2O16 Formula Weight 685.59 499.15 Temperature (K) 298(2) 100(2) Crystal System triclinic monoclinic Space group P -1 C 2/m a (Å) 6.8591(9) 8.8647(6) b (Å) 9.9691(13) 10.5247(7) c (Å) 10.9231(11) 21.2265(14) α 93.021(2)° 90° β 104.883(2)° 92.525(2)° γ 103.702(2)° 90° V (Å3) 696.16(16) 899.07(18) Z 1 2 Dcalc (Mg m-3) 1.636 1.844 Absorption coefficient, mm-1 1.292 1.087 F(000) 356.1 510.0 Crystal Size (mm) 0.38 × 0.21 × 0.17 0.41 × 0.15 × 0.17 θ range for data collection 0.860-28.29° 0.996-28.37° Reflections collected 5166 4732 Unique reflections 3450 1196 Parameters 253 109 Goodness-of-fit 1.197 1.098 Ra [I > 2σ(I )] 0.0386 0.0342 wRb (all data) 0.1072 0.0873 ___________________________________________________________________________________
a R = Σ( |Fo | – |Fc|)/Σ|Fo| b wR = (Σ[w( F o2 – Fc
2)2] /Σ[w(Fo2)2])1/2
Table 2. Atomic coordinates ( × 104) and equivalent isotropic displacement
parameters (Ǻ2 × 103) for (1). U(eq) is defined as one third of the trace of the
orthogonalized Uij tensor.
________________________________________________________________
x y z U(eq)
________________________________________________________________
Co(1) 10000 0 10000 20(1) Co(2) 0 5000 5000 33(1) C(1) 7051(4) 473(3) 4958(3) 25(1) C(2) 6611(4) 382(3) 6131(2) 23(1) C(3) 4542(4) -83(3) 6170(2) 23(1) C(5) 3994(4) -107(3) 7426(2) 25(1) O(1) 8407(3) -214(2) 8077(2) 25(1) O(2) 7634(4) -1690(2) 10255(2) 32(1) O(3) 2749(4) -1173(2) 7573(2) 41(1) O(4) 4782(3) 973(2) 8220(2) 30(1) O(5) 9682(4) 1867(2) 7533(2) 42(1) O(6) 8290(3) 1419(2) 10295(2) 29(1) O(7) -1697(5) 6483(3) 4989(3) 54(1) O(8) 2467(5) 6342(3) 6352(4) 64(1) O(9) 1033(6) 5838(3) 3476(3) 58(1) O(7B) 3030(30) 6050(20) 4990(20) 55(1) O(8B) -190(30) 6680(20) 6100(20) 64(1) O(9B) 1190(30) 5850(20) 3330(19) 58(1) O(10) 4990(5) 6503(3) 2919(3) 66(1) O(11) 6869(5) 6969(3) 7086(3) 66(1) O(12) 5260(20) 4518(12) 1043(11) 167(6) O(13) 7580(90) 5410(30) 9390(40) 220(30) O(14) 318(17) 5695(5) 9021(5) 197(6) ________________________________________________________________
Table 3. Selected bond lengths [Å] and angles [°] for (1).
_____________________________________________________________
Co(1)-O(1) 2.0778(18) Co(1)-O(6) 2.101(2) Co(1)-O(2) 2.130(2) Co(2)-O(8B) 2.062(19) Co(2)-O(8) 2.067(3) Co(2)-O(7) 2.086(3) Co(2)-O(7B) 2.10(2) Co(2)-O(9) 2.108(3) Co(2)-O(9B) 2.108(19) C(1)-H(1) 0.90(4) C(2)-C(1) 1.392(4) C(3)-C(2) 1.397(4) C(4)-O(5) 1.242(3) C(4)-C(2) 1.501(4) C(5)-O(3) 1.242(3) C(5)-O(4) 1.261(3) C(5)-C(3) 1.513(3) O(1)-C(4) 1.268(3) O(2)-H(2A) 0.74(4) O(2)-H(2B) 0.80(6) O(6)-H(6B) 0.77(5) O(6)-H(6A) 0.91(5) O(7)-H(7A) 0.8200 O(7)-H(7B) 0.827(19) O(7)-H(8D) 1.40(8) O(7B)-H(7C) 0.8200 O(7B)-H(7D) 0.819(10) O(8)-H(8A) 0.8200 O(8)-H(8B) 0.829(18) O(8B)-H(8C) 0.8200 O(8B)-H(8D) 0.821(11) O(9)-H(9A) 0.8200 O(9)-H(9B) 0.843(19) O(9B)-H(9C) 0.8200 O(9B)-H(9D) 0.820(11) O(10)-H(10A) 0.893(19) O(10)-H(10B) 0.900(19) O(11)-H(11A) 0.886(19) O(11)-H(11B) 0.891(19) O(12)-H(12A) 0.91(2) O(12)-H(12B) 0.91(2) O(14)-H(14A) 0.9030 O(14)-H(14B) 0.9013
C(2)-C(3)-C(5) 121.1(2) O(1)-Co(1)-O(6) 87.01(8) O(1)-Co(1)-O(2) 89.40(8) O(6)-Co(1)-O(2) 91.12(9) O(8B)-Co(2)-O(8) 54.4(6) O(8B)-Co(2)-O(7) 38.0(6) O(8)-Co(2)-O(7) 88.69(13) O(8B)-Co(2)-O(7B) 90.6(7) O(8)-Co(2)-O(7B) 47.2(6) O(7)-Co(2)-O(7B) 107.4(5) O(8B)-Co(2)-O(9) 105.3(7) O(8)-Co(2)-O(9) 92.55(15) O(7)-Co(2)-O(9) 89.62(13) O(7B)-Co(2)-O(9) 51.0(6) O(8B)-Co(2)-O(9B) 90.9(8) O(8)-Co(2)-O(9B) 115.4(6) O(7)-Co(2)-O(9B) 58.4(6) O(7B)-Co(2)-O(9B) 88.7(7) O(9)-Co(2)-O(9B) 41.3(6) C(2)-C(1)-H(1) 123(2) C(1)-C(2)-C(3) 119.7(2) C(1)-C(2)-C(4) 119.5(2) C(3)-C(2)-C(4) 120.8(2) O(5)-C(4)-O(1) 125.1(2) O(5)-C(4)-C(2) 119.0(2) O(1)-C(4)-C(2) 115.9(2) O(3)-C(5)-O(4) 125.3(2) O(3)-C(5)-C(3) 117.3(2) O(4)-C(5)-C(3) 117.4(2) C(4)-O(1)-Co(1) 127.97(17) Co(1)-O(2)-H(2A) 114(3) Co(1)-O(2)-H(2B) 108(4) H(2A)-O(2)-H(2B) 106(5) Co(1)-O(6)-H(6B) 116(4) Co(1)-O(6)-H(6A) 111(3) H(6B)-O(6)-H(6A) 106(5) Co(2)-O(7)-H(7A) 109.5 Co(2)-O(7)-H(7B) 113(4) H(7A)-O(7)-H(7B) 129.6 Co(2)-O(7)-H(8D) 78(10) H(7A)-O(7)-H(8D) 84.5 H(7B)-O(7)-H(8D) 130(5) Co(2)-O(8)-H(8A) 109.5 Co(2)-O(8)-H(8B) 121(4) H(8A)-O(8)-H(8B) 128.5 Co(2)-O(9)-H(9A) 109.5
Co(2)-O(7B)-H(7C) 109.5 Co(2)-O(7B)-H(7D) 111(10) H(7C)-O(7B)-H(7D) 130.3 Co(2)-O(8B)-H(8C) 109.4 Co(2)-O(8B)-H(8D) 92(10) H(8C)-O(8B)-H(8D) 129.9 Co(2)-O(9B)-H(9C) 109.5 H(10A)-O(10)-H(10B) 101(3) H(11A)-O(11)-H(11B) 103(3) H(12A)-O(12)-H(12B) 99(3) H(14A)-O(14)-H(14B) 100.9 _____________________________________________________________
Table 4. Anisotropic displacement parameters [Å2 × 103] for (1). The anisotropic
displacement factor exponent takes the form: -2 π2 [(h a*)2 U11 + ... + 2 h k a* b* U12]
_______________________________________________________________________
U11 U22 U33 U23 U13 U12
_______________________________________________________________________
Co(1) 22(1) 26(1) 12(1) 4(1) 3(1) 7(1) Co(2) 38(1) 27(1) 32(1) 6(1) 8(1) 8(1) O(1) 29(1) 30(1) 14(1) 6(1) 2(1) 9(1) O(2) 30(1) 38(1) 27(1) 6(1) 10(1) 6(1) O(3) 53(1) 43(1) 24(1) 1(1) 22(1) -4(1) O(4) 32(1) 38(1) 20(1) 0(1) 8(1) 11(1) O(5) 39(1) 40(1) 30(1 15(1) -7(1) -5(1) O(6) 34(1) 40(1) 18(1) 6(1) 10(1) 15(1) C(1) 23(1) 35(1) 17(1) 5(1) 5(1) 6(1) C(2) 25(1) 29(1) 14(1) 5(1) 4(1) 8(1) C(3) 27(1) 31(1) 13(1) 6(1) 7(1) 9(1) C(4) 25(1) 33(1) 14(1) 4(1) 4(1) 8(1) C(5) 25(1) 37(1) 14(1) 4(1) 5(1) 11(1) O(7) 61(2) 55(2) 54(2) 9(1) 11(2) 32(2) O(8) 48(2) 47(2) 80(2) -17(2) -3(2) 10(1) O(9) 73(2) 50(2) 67(2) 28(2) 36(2) 27(2) O(7B) 61(2) 55(2) 54(2) 9(1) 11(2) 32(2) O(8B) 48(2) 47(2) 80(2) -17(2) -3(2) 10(1) O(9B) 73(2) 50(2) 67(2) 28(2) 36(2) 27(2) O(10) 72(2) 57(2) 71(2) 23(2) 19(2) 23(2) O(11) 73(2) 44(2) 73(2) -7(1) 8(2) 15(1) O(12) 202(13) 128(8) 146(9) -21(6) 60(8) -9(7) O(13) 310(50) 150(30) 190(30) 30(20) 80(30) 40(20) O(14) 397(15) 64(3) 81(4) -2(3) 65(6) -30(5) _______________________________________________________________________
Table 5. Hydrogen coordinates (× 104) and isotropic displacement parameters
(Å2 × 103) for (1).
________________________________________________________________
x y z U(eq)
________________________________________________________________
H(1) 8360(60) 670(40) 4880(30) 36(9) H(2A) 6800(70) -1470(40) 10470(40) 41(11) H(2B) 8210(100) -2040(60) 10840(60) 100(20) H(6A) 7090(70) 1280(40) 9660(50) 55(12) H(6B) 7960(80) 1390(50) 10910(50) 74(16) H(7A) -1962 6562 5675 82 H(7B) -2470(70) 6530(70) 4300(20) 82 H(7C) 3824 5554 5223 82 H(7D) 3400(200) 6890(60) 5200(300) 82 H(8A) 2032 6904 6711 95 H(8B) 3710(40) 6370(60) 6480(60) 95 H(8C) 233 6592 6861 95 H(8D) 400(400) 7300(300) 5770(110) 95 H(9A) 764 6592 3389 87 H(9B) 2150(60) 5730(50) 3340(60) 87 H(9C) -1832 6406 3492 87 H(9D) -100(300) 6090(70) 3200(400) 87 H(10A) 5040(100) 6070(50) 2200(30) 98 H(10B) 4940(90) 7350(30) 2690(50) 98 H(11A) 7960(60) 6740(50) 7580(50) 99 H(11B) 7100(80) 7860(30) 7360(50) 99 H(12A) 5200(300) 4000(170) 330(110) 250 H(12B) 6600(120) 5040(180) 1250(170) 250 H(14A) 1553 5503 9059 296 H(14B) 753 6566 9432 296 ________________________________________________________________
Table 6. Hydrogen Bonding Geometry Parameters in the structure of (1). Specified
hydrogen bonds with H..A < r(A) + 2.000 Angstroms (with esds except for fixed and
riding H). Hydrogen bonds to the minor occupied cobalt-hexaaqua complex are omitted.
D-H···A D-H (Å) H···A (Å) D···A (Å) D-H···A (deg) O2-H2A···O4a O2-H2B···O5h O6-H6B···O3a O6-H6A···O4 O7m-H7Am···O11 O7m-H7Bm···O10 O8-H8B···O11 O8-H8A···O3e O9-H9A···O5j O10-H10A···O12 O10-H10B···O4f O11-H11A···O14m O11-H11B···O1b O12-H12A···O2k O12-H12A···O12i O14-H14B···O6c
0.74(4) 0.80(6) 0.77 0.91 0.82 0.83(2) 0.83(2) 0.82 0.82 0.89 0.90(2) 0.89(2) 0.89(2) 0.91(2) 0.91(2) 0.90
2.11(4) 1.95(6) 1.85(5) 1.87(5) 1.98 1.20(3) 2.04(3) 1.98 1.92 2.00 1.98(3) 2.42(2) 1.94(3) 2.58(15) 2.2(2) 1.94
2.807(3) 2.677(3) 2.612(3) 2.777(3) 2.777(5) 2.769(5) 2.822(5) 2.691(4) 2.685(4) 2.846(11) 2.854(4) 3.289(10) 2.803(3) 3.063(10) 2.49(3) 2.803(5)
157(4) 150(6) 175(6) 173(4) 165 162(5) 164(5) 144 154 157 162(5) 166(1) 164(5) 114(12) 99(14) 159
Note: Symmetry codes: (a) -x+1, -y,-z+2; (b) x, y+1, z; (c) -x+1, -y+1, -z+2; (d) x+1, y, z; (e) x, y+1, z; (f) -x+1, -y+1, -z+1; (g) -x+2, -y+1, -z+1; (h) -x+2, -y, -z+2; (i) -x+1, -y+1, -z; (j) -x+1, -y+1, -z+1; (k) -x+1, -y, -z+1; (l) -x+1, -y+1, -z+1; (m) x+1, -y+1, -z+1
Table 7. Atomic coordinates (× 104) and equivalent isotropic displacement
parameters (Ǻ2 × 103) for (2). U(eq) is defined as one third of the trace of the
orthogonalized Uij tensor.
________________________________________________________________ x y z U(eq) ________________________________________________________________ Co(1) 10000 10000 10000 8(1) Na(1A) 7496(2) 7673(120) 5163(4) 16(1) C(1) 9731(1) 6264(2) 5893(3) 11(1) C(2) 9460(1) 5000 6760(4) 12(1) C(4) 9482(1) 7596(2) 7021(3) 16(1) O(1) 10084(1) 8394(1) 7652(2) 16(1) O(2) 11369(1) 10000 10135(3) 11(1) O(3) 8679(2) 7608(3) 7738(5) 14(1) O(4) 8190(4) 6887(4) 1892(9) 26(1) O(5) 7058(1) 5000 5979(3) 18(1) O(6) 6749(4) 8660(5) 8150(11) 26(1) O(7) 6271(3) 7048(4) 3060(6) 14(1)
Table 8. Selected bond lengths [Å] and angles [°] for (2).
_____________________________________________________________
Co(1)-O(1) 2.1003(12) Co(1)-O(2) 2.126(2) O(1)-C(4) 1.254(3) O(2)-H(2) 0.87(3) C(1)-C(4) 1.502(3) C(2)-C(1) 1.388(2) C(2)-H(2B) 0.95(5) C(4)-O(3) 1.340(5) Na(1)-O(3) 2.361(5) Na(1)-O(4) 2.419(6) Na(1)-O(5) 2.691(2) Na(1)-O(6) 2.388(6) Na(1)-O(7) 2.323(5) O(4)-H(4A) 0.90(3) O(4)-H(4B) 0.87(3) O(5)-H(5B) 0.83(3) O(5)-H(5A) 0.87(3) O(6)-H(6A) 0.89(3) O(6)-H(6B) 0.88(3) O(1)-Co(1)-O(2) 86.21(6) C(4)-O(1)-Co(1) 125.61(14) C(2)-C(1)-C(4) 118.31(18) C(1)-C(2)-H(2B) 119.69(13) O(1)-C(4)-O(3) 126.1(2) O(1)-C(4)-C(1) 116.71(18) O(3)-C(4)-C(1) 114.7(2) O(7)-Na(1)-O(3) 162.30(17) O(7)-Na(1)-O(6) 96.0(2) O(3)-Na(1)-O(6) 84.2(2) O(7)-Na(1)-O(4) 81.6(2) O(3)-Na(1)-O(4) 99.9(2) O(6)-Na(1)-O(4) 173.6(3) O(7)-Na(1)-O(5) 69.51(12) O(3)-Na(1)-O(5) 92.84(13) O(6)-Na(1)-O(5) 95.68(17) O(4)-Na(1)-O(5) 89.01(16) Co(1)-O(2)-H(2) 102(2) C(4)-O(3)-Na(1) 119.7(2) Na(1)-O(4)-H(4A) 115(2) Na(1)-O(4)-H(4B) 118(2) H(4A)-O(4)-H(4B) 101(4) Na(1)-O(5)-H(5B) 104.1(6)
Na(1)-O(5)-H(5A) 97.2(8) H(5B)-O(5)-H(5A) 107(4) Na(1)-O(6)-H(6A) 120(2) Na(1)-O(6)-H(6B) 120(2) H(6A)-O(6)-H(6B) 101(3) _____________________________________________________________
Table 9. Anisotropic displacement parameters [Å2 × 103] for (2). The anisotropic
displacement factor exponent takes the form: -2 π2 [(h a*)2 U11 + ... + 2 h k a* b* U12]
_______________________________________________________________________
U11 U22 U33 U23 U13 U12
_______________________________________________________________________
Co(1) 9(1) 7(1) 8(1) 0 1(1) 0 C(1) 11(1) 11(1) 13(1) -2(1) -1(1) 1(1) C(2) 11(1) 16(1) 10(1) 0 2(1) 0 C(4) 15(1) 13(1) 19(1) -6(1) -4(1) 4(1) O(1) 18(1) 16(1) 14(1) -6(1) 4(1) -5(1) O(2) 13(1) 8(1) 11(1) 0 0(1) 0 O(3) 11(1) 12(1) 18(2) -3(1) 2(1) -1(1) O(4) 26(1) 32(2) 20(1) -7(2) 1(1) 12(2) O(5) 20(1) 20(1) 13(1) 0 3(1) 0 O(6) 26(1) 32(3) 20(1) -7(2) 1(1) 12(2) O(7) 11(1) 12(2) 18(2) -3(1) 2(1) -1(1) _______________________________________________________________________
Table 10. Hydrogen coordinates (× 104) and isotropic displacement parameters (Å2 ×
103) for (2).
________________________________________________________________
x y z U(eq)
________________________________________________________________
H(2) 11490(20) 10730(30) 10950(50) 27 H(2B) 9080(30) 5000 7940(80) 27 H(4A) 8130(40) 5960(40) 1590(90) 39 H(4B) 8750(20) 6980(70) 1860(70) 39 H(5A) 6570(20) 5000 5230(60) 27 H(5B) 6950(30) 5000 7310(40) 27 H(6A) 6770(40) 8230(60) 9450(50) 39 H(6B) 6200(20) 8860(70) 7990(60) 39
Table 11. Hydrogen Bonding Geometry Parameters in the structure of (2). Specified
hydrogen bonds with H..A < r(A) + 2.000 Angstroms (with esds except for riding H).
D-H···A D-H (Å) H···A (Å) D···A (Å) D-H···A (deg) O2-H2···O3a O2-H2···O7b O4-H4A···O6d O4-H4B···O1c
O5-H5A···O7 O5-H5A···O7f O5-H5B···O2e O6-H6A···O3g O6-H6A···O7h
0.87 0.87 0.90 0.87 0.87 0.87 0.83 0.83 0.89
1.80 1.84 2.21 2.27 2.390 2.390 1.97 2.04 2.61
2.624(4) 2.648(4) 3.081(7) 3.045(7) 2.875(4) 2.875(4) 2.783(3) 2.877(7) 3.462(7)
158 155 161 148 115.8 115.8 165 158 161
Note: Symmetry codes: (a) -x+2, -y+2, -z+2; (b) x+1/2, y+1/2, z+1; (c) -x+2, y, -z+1;
(d) -x+3/2, y-1/2, -z+1; (e) x-1/2, y-1/2, z; (f) x, -y+1, z; (g) -x+3/2, -y+3/2, -z+2; (h) x,
y, z+1
Figure 1. A thermal ellipsoid plot of the structure of
[Co(OH)2(H2O)4][Co(BTCA)(H2O)4]•7.2H2O (1). Solvent water molecules were omitted
for the sake of clarity and only one set of disordered ligands around Co2 are shown.
Atoms are shown at the 50% probability level.
Figure 2. A packing diagram illustrating the unit cell of (1) as well as the extended
structure of as viewed down the a axis. Solvent water molecules were omitted for clarity.
Figure 3. A representation of the hydrogen bonding interactions in (1).
Figure 4. A thermal ellipsoid plot of the structure of [Na2Co(H2O)4(µ-H2O)2(µ-BTCA)]
(2). Atoms are shown at the 50% probability level.
Two more pictures to choose from: