Azobispyrazole Family as Photoswitches Combining (Near ...

doi.org/10.26434/chemrxiv.14130095.v2

Azobispyrazole Family as Photoswitches Combining (Near-)QuantitativeBidirectional Isomerization and Widely Tunable Thermal Half-Lives fromHours to YearsYixin He, Zhichun Shangguan, Zhao-Yang Zhang, Mingchen Xie, Chunyang Yu, Tao LI

Submitted date: 03/03/2021 • Posted date: 03/03/2021Licence: CC BY-NC-ND 4.0Citation information: He, Yixin; Shangguan, Zhichun; Zhang, Zhao-Yang; Xie, Mingchen; Yu, Chunyang; LI,Tao (2021): Azobispyrazole Family as Photoswitches Combining (Near-)Quantitative BidirectionalIsomerization and Widely Tunable Thermal Half-Lives from Hours to Years. ChemRxiv. Preprint.https://doi.org/10.26434/chemrxiv.14130095.v2

Azobenzenes are classical molecular photoswitches that have received widespread application. In recentendeavors of molecular design, replacing one or both phenyl rings by heteroaromatic ones is emerging as astrategy to expand the molecular diversity and to access improved photoswitch properties. However, thecurrently available heteroaryl azo switches generally show limitations on E ⇆ Z photoisomerization yieldsand/or Z-isomer stability. Here we report a family of azobispyrazoles as new photoswitches, which combine(near-)quantitative bidirectional photoconversions and widely tunable Z-isomer thermal half-lives (t1/2) fromhours to years. A visible-light-activated photoswitch is also obtained. Systematic experimental and theoreticalinvestigations reveal the different geometric and electronic structures of azobispyrazoles from those ofphenylazopyrazoles, overcoming the conflict existing in the latter between effective photoconversion andZ-isomer stability. Our work shows the great potential of azobispyrazoles in developing photoresponsivesystems and can inspire the rational design of new photoswitches making use of bis-heteroaryl azoarchitecture.

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http://doi.org/10.26434/chemrxiv.14130095.v2

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Azobispyrazole family as photoswitches combining

(near-)quantitative bidirectional isomerization and widely

tunable thermal half-lives from hours to years

Supporting Information

Yixin He, Zhichun Shangguan, Zhao-Yang Zhang,* Mingchen Xie, Chunyang Yu, and Tao Li*

School of Chemistry and Chemical Engineering, Frontiers Science Center for Transformative Molecules,

Shanghai Key Laboratory of Electrical Insulation and Thermal Aging, Shanghai Jiao Tong University,

Shanghai 200240, China

Table of Contents

1. Synthesis ...................................................................................................................................................... 1

1.1 General methods ................................................................................................................................ 1

1.2 Synthetic procedures ......................................................................................................................... 1

2. Photoswitching performance ....................................................................................................................... 5

2.1 Quantification of PSS composition by NMR .................................................................................... 5

2.2 Calculation of PSS composition by UV-Vis spectroscopy .............................................................. 12

2.3 Quantum yields of photoisomerization ............................................................................................ 13

2.4 Cycling stability of photoswitching ................................................................................................. 16

3. Thermal isomerization kinetics ................................................................................................................. 17

4. X-ray crystallography ................................................................................................................................ 23

5. Computational details ................................................................................................................................ 29

Cartesian coordinates for optimized geometries (in acetonitrile) .......................................................... 48

References ..................................................................................................................................................... 73

1

1. Synthesis

1.1 General methods

All reagents and solvents were obtained commercially (Bide Pharmatech Ltd, Shanghai Titan Technology

Ltd, and J&K Scientific Ltd). All reactions were monitored by thin-layer chromatography (TLC) performed

on silica gel F254 coated glass plates (HSGF254, Huanghai) and visualized by irradiation under UV light

(254 nm). Column chromatography was performed using silica gel (300-400 mesh, Huanghai).

1H NMR and 13C NMR spectra were recorded on Bruker AVANCE III HD 400 spectrometers at 400 MHz

and 101 MHz, respectively. Chemical shifts (δ) were internally referenced to residual solvent signals: 1H δ =

7.26 (CDCl3), 4.79 (D2O), 2.50 (DMSO-d6) ppm; 13C δ = 77.06 (CDCl3), 39.53 (DMSO-d6) ppm.1 HRMS

data were obtained on Bruker Impact II quadrupole time of flight mass spectrometry instrument. UV-Vis

absorption spectra were recorded on Shimadzu UV-2700 spectrophotometer with slit width of 2.0 nm.

Melting points (m.p.) were determined on SGW X-4B digital melting point apparatus (Shanghai INESA

Physical Optics Instrument Ltd).

1.2 Synthetic procedures

Malonaldehyde sodium salt (MDA-Na)

The synthesis of malonaldehyde sodium salt (MDA-Na) followed the method from literature.2

1H NMR (400 MHz, D2O) δ 8.66 (d, J = 10.1 Hz, 2H), 5.31 (t, J = 10.1 Hz, 1H); 13C NMR (101 MHz, D2O)

δ 193.30, 109.91.

2-(2-(1-methyl-1H-pyrazol-3-yl)hydrazineylidene)malonaldehyde (3-HM)

1-methyl-1H-pyrazol-3-amine (971 mg, 10 mmol, 1 eq.) was dissolved in AcOH (15 mL) and concentrated

HCl (2.3 mL) at 0 °C, followed by slowly adding a prechilled solution of NaNO2 (828 mg, 12 mmol, 1.2 eq.)

in a minimum amount of water. The mixture was stirred for 30 min at 0 °C. Then a prechilled solution of

KOAc (2.94 g, 30 mmol, 3 eq.) in a minimum amount of water and MDA-Na (1.41 g, 15 mmol, 1.5 eq.)

solids were added in sequence. After the mixture was stirred for 1.5 h at 0–5 °C, the resulting precipitate was

2

filtered and washed with water. The filter cake was dried under vacuum, affording the desired product as

yellow solids (966 mg, 54%).

1H NMR (400 MHz, CDCl3) δ 14.58 (s, 1H), 9.96 (s, 1H), 9.58 (s, 1H), 7.34 (d, J = 2.3 Hz, 1H), 6.42 (d, J =

2.3 Hz, 1H), 3.88 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 189.73, 186.41, 151.08, 133.35, 132.30, 94.98,

39.41; HRMS (ESI) m/z calculated for [C7H8N4O2+H]+ 181.0720, found 181.0718.

(E)-1-methyl-4-((1-methyl-1H-pyrazol-3-yl)diazenyl)-1H-pyrazole (3-4)

Methylhydrazine sulfate (173 mg, 1.2 mmol, 1.2 eq.) and KOAc (236 mg, 2.4 mmol, 2.4 eq.) were added to

a solution of 3-HM (180 mg, 1 mmol, 1 eq.) in EtOH (10 mL). The reaction mixture was refluxed for 4 hours,

and then quenched by adding water and extracted with EA for 3 times. The combined organic layers were

washed by brine, dried over anhydrous Na2SO4, and concentrated under reduced pressure to afford the desired

product as yellow solids (152 mg, 80%).

1H NMR (400 MHz, CDCl3) δ 8.02 (s, 1H), 7.94 (s, 1H), 7.35 (d, J = 2.4 Hz, 1H), 6.53 (d, J = 2.4 Hz, 1H),

3.97 (s, 3H), 3.94 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 163.70, 141.96, 133.89, 131.73, 126.49, 96.00,

39.64, 39.56; HRMS (ESI) m/z calculated for [C8H10N6+H]+ 191.1040, found 191.1040; UV-Vis (MeCN)

λmax = 326 nm; m.p. 135–136 °C.

2-(2-(1-methyl-1H-pyrazol-4-yl)hydrazineylidene)malonaldehyde (4-HM)

1-methyl-1H-pyrazol-4-amine (971 mg, 10 mmol, 1 eq.) was dissolved in AcOH (15 mL) and concentrated

HCl (2.3 mL) at 0 °C, followed by slowly adding a prechilled solution of NaNO2 (828 mg, 12 mmol, 1.2 eq.)

in a minimum amount of water. The mixture was stirred for 30 min at 0 °C. Then a prechilled solution of

KOAc (2.94 g, 30 mmol, 3 eq.) in a minimum amount of water and MDA-Na (1.41 g, 15 mmol, 1.5 eq.)

solids were added in sequence. After the mixture was stirred for 1.5 h at 0–5 °C, the resulting precipitate was

filtered and washed with water. The filter cake was dried under vacuum, affording the desired product as

yellow solids (920 mg, 51%).

1H NMR (400 MHz, CDCl3) δ 14.70 (s, 1H), 9.89 (s, 1H), 9.52 (s, 1H), 7.66 (s, 1H), 7.63 (s, 1H), 3.94 (s,

3

3H); 13C NMR (101 MHz, CDCl3) δ 189.28, 186.26, 133.34, 129.82, 127.51, 120.61, 39.80; HRMS (ESI)

m/z calculated for [C7H8N4O2+H]+ 181.0720, found 181.0721.

(E)-1,2-bis(1-methyl-1H-pyrazol-4-yl)diazene (4-4)

Methylhydrazine sulfate (173 mg, 1.2 mmol, 1.2 eq.) and KOAc (236 mg, 2.4 mmol, 2.4 eq.) were added to

a solution of 4-HM (180 mg, 1 mmol, 1 eq.) in EtOH (10 mL). The reaction mixture was refluxed for 4 hours,

and then quenched by adding water and extracted with EA for 3 times. The combined organic layers were

washed by brine, dried over anhydrous Na2SO4, and concentrated under reduced pressure to afford the desired

product as yellow solids (123 mg, 65%).

1H NMR (400 MHz, CDCl3) δ 7.89 (s, 2H), 7.83 (s, 2H), 3.93 (s, 6H); 13C NMR (101 MHz, CDCl3) δ 141.86,

132.80, 125.99, 39.55; HRMS (ESI) m/z calculated for [C8H10N6+H]+ 191.1040, found 191.1040; UV-Vis

(MeCN) λmax = 327 nm; m.p. 176–177 °C.

2-(2-(1H-pyrazol-3(5)-yl)hydrazineylidene)malonaldehyde (3(5)-HM)

1H-pyrazol-3(5)-amine (2.49 g, 30 mmol, 1 eq.) was dissolved in AcOH (45 mL) and concentrated HCl (6.9

mL) at 0 °C, followed by slowly adding a prechilled solution of NaNO2 (2.48 g, 36 mmol, 1.2 eq.) in a

minimum amount of water. The mixture was stirred for 30 min at 0 °C. Then a prechilled solution of KOAc

(8.83 g, 90 mmol, 3 eq.) in a minimum amount of water and MDA-Na (4.23 g, 45 mmol, 1.5 eq.) solids were

added in sequence. After the mixture was stirred for 1.5 h at 0–5 °C, the resulting precipitate was filtered and

washed with water. The filter cake was dried under vacuum, affording the desired product as yellow solids

(1.98 g, 40%).

1H NMR (400 MHz, DMSO-d6) δ 9.52 (s, 1H), 7.56 (d, J = 2.0 Hz, 1H), 6.46 (s, 1H), 5.88 (d, J = 2.0 Hz,

1H); 13C NMR (101 MHz, DMSO-d6) δ 189.16, 140.40, 137.56, 136.84, 87.36, 68.75; HRMS (ESI) m/z

calculated for [C6H6N4O2+H]+ 167.0564, found 167.0564.

(E)-1-methyl-4-(1H-pyrazol-3(5)-yl)diazenyl)-1H-pyrazole (4-3(5)-H)

4

Methylhydrazine sulfate (865 mg, 6 mmol, 1.2 eq.) and KOAc (1.178 g, 12 mmol, 2.4 eq.) were added to a

solution of 4-3(5)-H (830 mg, 5 mmol, 1 eq.) in EtOH (30 mL). The reaction mixture was refluxed for 4

hours, and then quenched by adding water and extracted with EA for 3 times. The combined organic layers

were washed by brine, dried over anhydrous Na2SO4, and concentrated under reduced pressure. The crude

product was purified by recrystallization (PE/DCM/EtOH) to afford the desired product as yellow solids (672

mg, 76%).

1H NMR (400 MHz, DMSO-d6) δ 13.24 (s, 1H), 8.42 (s, 1H), 7.94 (s, 1H), 7.80 (dd, J = 2.5, 1.5 Hz, 1H),

6.42 (t, J = 2.2 Hz, 1H), 3.91 (s, 3H); 13C NMR (101 MHz, DMSO-d6) δ 164.06, 141.09, 132.15, 130.38,

127.93, 93.06, 39.20; HRMS (ESI) m/z calculated for [C7H8N6+H]+ 177.0883, found 177.0884.


Cs2CO3 (652 mg, 2 mmol, 2 eq.) and CH3I (284 mg, 1.5 mmol, 1.5 eq.) were successively added into a

solution of 4-3(5)-H (176 mg, 1 mmol, 1 eq.) in DMF (10 mL). The reaction mixture was stirred at room

temperature for 5 h, and then quenched by adding water and extracted with EA for 3 times. The combined

organic layers were washed by brine, dried over anhydrous Na2SO4, and concentrated under reduced

pressure. The crude product was purified by column chromatography (PE:EA = 1:1 to 1:2) to afford the

desired product as yellow solids (4-5 85 mg, 45%; 3-4 72 mg, 38%).

4-5: 1H NMR (400 MHz, CDCl3) δ 7.97 (s, 2H), 7.51 (d, J = 2.2 Hz, 1H), 6.44 (d, J = 2.2 Hz, 1H), 4.15 (s,

3H), 3.98 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 153.29, 142.21, 139.09, 132.83, 127.70, 93.22, 39.73, 35.94;

HRMS (ESI) m/z calculated for [C8H10N6+H]+ 191.1040, found 191.1041; UV-Vis (MeCN) λmax = 342 nm;

m.p. 126–128 °C.




5

3(5)-2H was synthesized via oxidizative coupling of 1H-pyrazol-3-amine by MnO2, following the

procedure reported in literature.3,4 Cs2CO3 (6.52 g, 20 mmol, 4 eq.) and CH3I (2.13 g, 15 mmol, 3 eq.) were

successively added into a solution of 3(5)-2H (811 mg, 5 mmol, 1 eq.) in DMF (40 mL). The reaction

mixture was stirred at room temperature for 5 h, and then quenched by adding water and extracted with EA

for 3 times. The combined organic layers were washed by brine, dried over anhydrous Na2SO4, and

concentrated under reduced pressure. The crude product was purified by column chromatography (PE:EA =

1:1 to 1:2) to afford the desired product as yellow solids.

3-3 (142 mg, 15%): 1H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 2.0 Hz, 2H), 6.68 (d, J = 2.1 Hz, 2H), 4.00

(s, 6H); 13C NMR (101 MHz, CDCl3) δ 164.05, 131.83, 95.31, 39.60; HRMS (ESI) m/z calculated for

[C8H10N6+H]+ 191.1040, found 191.1040; UV-Vis (MeCN) λmax = 325 nm; m.p. 205–206 °C.

3-5 (437 mg, 46%): 1H NMR (400 MHz, CDCl3) δ 7.54 (d, J = 2.2 Hz, 1H), 7.40 (d, J = 2.5 Hz, 1H), 6.62 (d,

J = 2.2 Hz, 1H), 6.60 (d, J = 2.5 Hz, 1H), 4.19 (s, 3H), 4.03 (s, 3H); 13C NMR (101 MHz, CDCl3) δ 164.09,

153.31, 139.22, 132.01, 95.48, 94.33, 39.80, 36.11; HRMS (ESI) m/z calculated for [C8H10N6+H]+ 191.1040,

found 191.1040; UV-Vis (MeCN) λmax = 342 nm; m.p. 101–103 °C.

5-5 (228 mg, 24%): 1H NMR (400 MHz, CDCl3) δ 7.55 (d, J = 1.8 Hz, 2H), 6.54 (d, J = 2.0 Hz, 2H), 4.17 (s,

6H); 13C NMR (101 MHz, CDCl3) δ 153.52, 139.30, 93.96, 36.13; HRMS (ESI) m/z calculated for

[C8H10N6+H]+ 191.1040, found 191.1040; UV-Vis (MeCN) λmax = 356 nm; m.p. 139–140 °C.

2. Photoswitching performance

A multi-wavelength LED light source (Beijing NBET Technology Ltd) was used for photoisomerization.

2.1 Quantification of PSS composition by NMR

1H NMR spectra were recorded on Bruker AVANCE III HD 400 spectrometers at 400 MHz. Chemical shifts

(δ) were internally referenced to the CD3CN solvent signal (δ = 1.94 ppm).1 The photostationary state (PSS)

compositions were quantified by integrating spectra peak areas of E and Z isomers.

6

Figure S1. 1H NMR spectra of E-3-3 and its PSSs in CD3CN.

7

Figure S2. 1H NMR spectra of E-3-4 and its PSS in CD3CN.

8


9


10


11


12

2.2 Calculation of PSS composition by UV-Vis spectroscopy

UV-Vis absorption spectra were recorded on Shimadzu UV-2700 spectrophotometer with slit width of 2.0

nm. The solvent used was of spectrophotometric grade. PSS compositions at different wavelengths were

calculated according to the reported method.5,6

Figure S7. UV-Vis spectra of azobispyrazoles at PSSs in MeCN (4×10-5 mol/L).

13

2.3 Quantum yields of photoisomerization

The differential rate equation of E→Z photoisomerization is as following:7-9

1 0 1( )tt t

dck c c k c

dt−= − −

( )

1

(1 10 )

( )

A t

E Z EI lk

V A t

−

→ − =

( )

1

(1 10 )

( )

A t

Z E ZI lk

V A t

−

→−

− =

where k1 and k-1 are the rate constants at the excitation wavelength of E→Z and Z→E isomerization,

respectively; c0 = [E]0 is the initial concentration of E-isomer, ct = [Z]t is the concentration of Z-isomer at

time t; I is the photon flux of the excitation light; l is the beam path length through quartz cuvette; A(t) is the

absorbance with time t at the excitation wavelength; ΦE→Z and ΦZ→E are quantum yields at the excitation

wavelength of E→Z and Z→E isomerization, respectively; εE and εZ are the absorption coefficients at the

excitation wavelength of the E and Z isomer, respectively; V is the volume of irradiated solution.

At the PSS, the concentrations of both isomers do not change any more, i.e. 0tdc

dt= .

Thus, the equation 0( )

E Z Z

Z E E

c

c c

→

→

=

− is obtained, where c∞ = [Z]∞ is the concentration of Z-isomer at

the PSS. Defining the fraction of Z-isomer as y = ct / c0 (calculated from UV-Vis spectra), the equations

depicted above are combined as

0

( )

0

1 10ln

( )

A tt

E Z E

t

I ly ydt

y y V y A t

−

→

− −= −

−

where y∞ = c∞ / c0 is the fraction of Z-isomer at the PSS.

Let the parameter E Z EI lB

V y

→

=

and integrated photokinetic factor

0

( )1 10( )

( )

A tt

tx t dt

A t

−−= , then

0( ) exp[ ( )]y y y B x t y = − − + .

Plotting y against x(t), followed by exponential fitting, the B and y∞ are obtained.

The quantum yield is allowed to be calculated as E Z

E

B V y

I l

→

=

.

Similarly, the quantum yield of Z→E photoisomerization can be calculated by exchanging “E” and “Z” in

the equations shown above.

The quantum yield experiments were started from either E-isomers or Z-rich mixtures (350 or 365 nm PSSs).

The irradiated solution was 2 mL with magnetic stirring, and the beam path length through quartz cuvette

was 1 cm. The absorbance with time t was recorded on Shimadzu UV-2700 spectrophotometer with slit width

of 2.0 nm.

15

Figure S8. Exponential fitting of the fractions of Z or E isomer against the integrated photokinetic factors x(t)

for azobispyrazoles.

Table S1. Photon flux of the excitation lights (determined by chemical actinometry10,11)

Wavelength (nm) 350 365 470

Photon flux (mol·s-1) 8.66 × 10-6 1.89 × 10-4 1.18 × 10-4

16

2.4 Cycling stability of photoswitching

Figure S9. Repeated cycles of photoswitching for azobispyrazoles in MeCN (4×10-5 mol/L).

17

3. Thermal isomerization kinetics

Thermal Z→E isomerization kinetics was studied using Shimadzu UV-2700 spectrophotometer equipped

with a programmable temperature controller (DCY-1006, Shanghai Sunny Hengping Scientific Instrument

Ltd) according to our previous paper.6

Figure S10. UV-Vis first-order kinetics analysis and Arrhenius plot for thermal Z→E isomerization of 3-3.

Table S2. Thermal isomerization kinetics results of 3-3 in DMSO.

Experimental Calculated

50 ºC 55 ºC 60 ºC 65 ºC 25 ºC

k (min-1) 1.48×10-4 2.51×10-4 4.41×10-4 7.51×10-4 k (min-1) 6.68×10-6 Ea (kJ/mol) 98.8

t1/2 (min) 4689 2763 1570 923 t1/2 (d) 72 ln A 23.8

18




65 ºC 70 ºC 75 ºC 80 ºC 25 ºC


t1/2 (min) 5398 3127 1810 1073 t1/2 (d) 623 ln A 25.0

19




35 ºC 40 ºC 45 ºC 50 ºC 25 ºC


t1/2 (min) 2471 1362 783 450 t1/2 (d) 6 ln A 24.3

20




65 ºC 70 ºC 75 ºC 80 ºC 25 ºC


t1/2 (min) 5545 3136 1857 1069 t1/2 (d) 681 ln A 25.5

21




45 ºC 50 ºC 55 ºC 60 ºC 25 ºC


t1/2 (min) 3016 1705 978 568 t1/2 (d) 25 ln A 24.6

22




25 ºC 30 ºC 35 ºC 40 ºC 25 ºC


t1/2 (min) 428 237 133 77 t1/2 (h) 7 ln A 25.3

23

4. X-ray crystallography

Crystallography data were acquired on Bruker D8 VENTURE single crystal x-ray diffractometer. The crystal

structures were solved and refined using SHELX programs12 called from ShelXle13 and Olex214 graphical

user interfaces.

Figure S16. Crystal structure of E-3-3 (ellipsoid model).

Table S8. Crystal data and structure refinement of E-3-3.

Empirical formula C8H10N6

Formula weight 190.22

Temperature 173(2) K

Wavelength 1.54178 Å

Crystal system, Space group Monoclinic, P 21/c

Unit cell dimensions

a = 7.6310(4) Å

b = 9.2352(5) Å

c = 7.1960(4) Å

α = 90°

β = 104.733(4)°

γ = 90°

Volume 490.46(5) Å3

Z, Density (calculated) 2, 1.288 Mg/m3

Absorption coefficient 0.719 mm-1

F(000) 200

Crystal size 0.20 × 0.20 × 0.20 mm

Theta range for data collection 5.996 to 68.401°

Index ranges -9 ≤ h ≤ 9, -11 ≤ k ≤ 11, -8 ≤ l ≤ 7

Reflections collected / unique 4869 / 903 (Rint = 0.0657)

Completeness to theta = 67.679 99.9%

Refinement method Full-matrix least-squares on F2

Data / restraints / parameters 903 / 0 / 65

Goodness-of-fit on F2 1.038

Final R indices [I > 2sigma(I)] R1 = 0.0412, wR2 = 0.1061

R indices (all data) R1 = 0.0572, wR2 = 0.1174

Largest diff. peak and hole 0.168 and -0.213 e.Å-3

24







Crystal system Orthorhombic

Space group P 21 21 21


a = 7.7120(2) Å

b = 10.7768(3) Å

c = 11.2005(3) Å

α = 90°

β = 90°

γ = 90°

Volume 930.88(4) Å3

Z 4

Density (calculated) 1.357 Mg/m3


F(000) 400

Crystal size 0.15 × 0.14 × 0.12 mm


Index ranges -9 ≤ h ≤ 9, -12 ≤ k ≤ 12, -12 ≤ l ≤ 13

Reflections collected 13499

Independent reflections 1702 (Rint = 0.0378)








25







Crystal system Monoclinic

Space group P 21/n


a = 10.676(3) Å

b = 6.1547(11) Å

c = 15.417(4) Å

α = 90°

β = 109.29(2)°

γ = 90°

Volume 956.1(4) Å3

Z 4



F(000) 400

Crystal size 0.24 × 0.20 × 0.20 mm


Index ranges -12 ≤ h ≤ 12, -7 ≤ k ≤ 7, -17 ≤ l ≤ 18










26








Space group P 21/c


a = 7.16530(10) Å

b = 10.1213(2) Å

c = 7.15980(10) Å

α = 90°

β = 110.3820(10)°

γ = 90°

Volume 486.735(14) Å3

Z 2



F(000) 200

Crystal size 0.18 × 0.16 × 0.12 mm


Index ranges -8 ≤ h ≤ 8, -12 ≤ k ≤ 12, -8 ≤ l ≤ 8










27








Space group P 21


a = 4.1076(19) Å

b = 12.153(4) Å

c = 9.714(4) Å

α = 90°

β = 97.03(3)°

γ = 90°

Volume 481.3(3) Å3

Z 2



F(000) 200

Crystal size 0.2 × 0.2 × 0.2 mm


Index ranges -4 ≤ h ≤ 4, -14 ≤ k ≤ 14, -10 ≤ l ≤ 11

Reflections collected / unique 2972









28








Space group P 21/c


a = 7.9085(9) Å

b = 7.1007(8) Å

c = 9.0470(9) Å

α = 90°

β = 108.667(5)°

γ = 90°

Volume 481.32(9) Å3

Z 2



F(000) 200

Crystal size 0.25 × 0.24 × 0.2 mm


Index ranges -9 ≤ h ≤ 7, -7 ≤ k ≤ 8, -10 ≤ l ≤ 10










29

5. Computational details

All the theoretical calculations were performed on Gaussian 16 program.15 The molecular geometries of

ground and transition states were optimized at PBE0-D3(BJ)/6-31G** level of theory16-18 using SMD

solvation model19 in acetonitrile and dimethyl sulfoxide, followed by vibrational frequency analysis to ensure

the reliability of the obtained minimum and saddle points on potential energy surfaces. The relaxed scans for

CNNC dihedral angle φ and two CNN bond angles θ were carried out at the same level to explore the

mechanism of thermal Z→E isomerization and obtain the initial geometries for transition states.

For ground-state E and Z isomers, three and four conformers were considered for the symmetric (3-3, 4-4, 5-

5) and asymmetric molecules (3-4, 3-5, 4-5), respectively, due to the rotation of pyrazole rings along C–N

bonds linked to the azo-group. Each Z-conformer generated two types of transition states because inversion

could occur in either one of the pyrazoles (the symmetric Z-conformers generated two identical transition

states). The energies in gas phase and solvation free energies (using SMD solvation model19) of each

conformer were computed at B2PLYP-D3(BJ)/def2-TZVP20,21 and M05-2X/6-31G*18,22 level of theory,

respectively. Then, the Boltzmann distribution of all possible conformers and thermal Z→E isomerization

pathways were obtained according to the relative Gibbs free energies and the free energy barriers (ΔG‡),

respectively. The vertical electronic excitation energies for the ground-state geometries were calculated by

time-dependent density functional theory (TDDFT),23 and 20 lowest-lying singlet excited states were

considered at PBE0/6-31G** level of theory16,18 with SMD solvation model19 in acetonitrile. The natural

transition orbital (NTO)24 and noncovalent interaction (NCI)25 analysis were employed via Multiwfn

program,26 and the figures were rendered by VMD program.27

Table S14. Relative Gibbs free energies (Rel. Ggas and Gsoln), solvation free energies (ΔGsolv) and Boltzmann

distribution of ground-state conformers in solution (acetonitrile).

Conformation Rel. Ggas (1 atm)

(kcal/mol)

ΔGsolv (1 M)

(kcal/mol)

Rel. Gsoln (1 M)

(kcal/mol) Proportion (soln)

E-3-3

(1) 5.89 -19.53 4.12 0.09%

(2) 3.96 -19.01 2.71 1.01%

(3) 0.00 -17.76 0.00 98.90%

Z-3-3

(1) 0.00 -17.95 0.56 23.47%

(2) 0.30 -18.81 0.00 60.42%

(3) 1.68 -19.40 0.78 16.11%

E-3-4

(1) 0.00 -16.30 0.00 74.61%

(2) 0.45 -15.92 0.83 18.38%

(3) 2.24 -16.89 1.65 4.63%

(4) 2.64 -16.90 2.04 2.39%

30

Z-3-4

(1) 0.68 -16.67 0.68 13.27%

(2) 1.24 -17.31 0.60 15.19%

(3) 0.00 -16.67 0.00 41.57%

(4) 1.18 -17.65 0.19 29.97%

E-3-5

(1) 0.00 -14.82 0.00 71.50%

(2) 0.92 -14.00 1.74 3.78%

(3) 3.51 -15.12 3.22 0.31%

(4) 0.76 -14.94 0.64 24.41%

Z-3-5

(1) 2.37 -15.95 1.70 4.27%

(2) 1.58 -15.45 1.41 6.94%

(3) 0.37 -14.65 1.00 13.82%

(4) 0.00 -15.28 0.00 74.97%

E-4-4

(1) 0.44 -14.39 0.41 31.35%

(2) 0.00 -14.36 0.00 62.71%

(3) 1.16 -14.12 1.40 5.94%

Z-4-4

(1) 0.24 -15.37 0.44 30.65%

(2) 0.00 -15.56 0.00 64.15%

(3) 2.36 -16.43 1.49 5.20%

E-4-5

(1) 0.00 -13.29 0.00 67.42%

(2) 2.05 -13.08 2.26 1.48%

(3) 0.58 -13.40 0.47 30.60%

(4) 2.41 -12.79 2.90 0.50%

Z-4-5

(1) 0.00 -13.59 0.42 24.87%

(2) 0.08 -13.56 0.54 20.48%

(3) 0.21 -14.22 0.00 50.69%

(4) 1.21 -13.71 1.51 3.96%

E-5-5

(1) 0.00 -11.72 0.00 99.04%

(2) 3.09 -12.07 2.75 0.95%

(3) 5.09 -11.26 5.55 0.01%

Z-5-5

(1) 0.00 -11.58 0.00 87.83%

(2) 5.98 -11.80 5.76 0.005%

(3) 0.87 -11.28 1.17 12.16%

31

Table S15. Relative Gibbs free energies (Rel. Ggas and Gsoln), solvation free energies (ΔGsolv) and Boltzmann

distribution of ground-state conformers in solution (DMSO).

Conformation Rel. Ggas (1 atm)

(kcal/mol)

ΔGsolv (1 M)

(kcal/mol)

Rel. Gsoln (1 M)

(kcal/mol) Proportion (soln)

E-3-3

(1) 5.30 -17.07 3.52 0.26%

(2) 3.70 -16.55 2.44 1.60%

(3) 0.00 -15.29 0.00 98.14%

Z-3-3

(1) 0.00 -15.47 0.49 25.68%

(2) 0.42 -16.37 0.00 58.35%

(3) 1.88 -17.07 0.77 15.98%

E-3-4

(1) 0.00 -13.71 0.00 75.60%

(2) 0.46 -13.32 0.85 17.92%

(3) 2.26 -14.30 1.67 4.50%

(4) 2.76 -14.31 2.16 1.97%

Z-3-4

(1) 0.34 -14.16 0.62 13.83%

(2) 0.74 -14.84 0.33 22.28%

(3) 0.00 -14.16 0.27 24.78%

(4) 0.79 -15.22 0.00 39.11%

E-3-5

(1) 0.00 -12.32 0.00 79.34%

(2) 1.04 -11.52 1.84 3.56%

(3) 3.86 -12.65 3.53 0.21%

(4) 1.03 -12.44 0.92 16.90%

Z-3-5

(1) 2.45 -13.50 1.18 9.13%

(2) 2.07 -13.07 1.24 8.27%

(3) 0.00 -12.23 0.00 66.68%

(4) 1.50 -12.88 0.85 15.92%

E-4-4

(1) 0.38 -11.67 0.36 33.24%

(2) 0.00 -11.64 0.00 60.54%

(3) 1.10 -11.39 1.35 6.22%

Z-4-4

(1) 0.00 -12.77 0.00 39.98%

(2) 0.43 -12.97 0.23 27.11%

(3) 1.22 -13.88 0.12 32.91%

E-4-5

(1) 0.00 -10.67 0.00 67.39%

(2) 2.06 -10.50 2.23 1.56%

(3) 0.58 -10.78 0.47 30.53%

32

(4) 2.40 -10.20 2.87 0.52%

Z-4-5

(1) 0.05 -11.06 0.25 20.17%

(2) 0.00 -11.06 0.19 22.19%

(3) 0.48 -11.74 0.00 30.82%

(4) 0.02 -11.19 0.08 26.82%

E-5-5

(1) 0.00 -9.19 0.00 99.13%

(2) 3.23 -9.60 2.82 0.85%

(3) 4.73 -8.81 5.11 0.02%

Z-5-5

(1) 1.19 -9.15 0.87 18.74%

(2) 7.20 -9.44 6.59 0.001%

(3) 0.00 -8.83 0.00 81.25%

Table S16. Calculated excitation energies, excitation wavelengths (λ) and oscillator strengths (f) of

azobispyrazoles in solution (acetonitrile).

Conformation S0→S1 Excitation (n-π*) S0→S2 Excitation (π-π*)

Energy (eV) λ (nm) f Energy (eV) λ (nm) f

E-3-3

(1) 2.7390 452.66 0.0003 3.7746 328.47 0.8996

(2) 2.8485 435.26 0.0000 3.7859 327.49 0.8701

(3) 2.9582 419.12 0.0000 3.8036 325.96 0.8615

Z-3-3

(1) 2.6494 467.98 0.0595 3.9740 311.99 0.0665

(2) 2.7587 449.43 0.0489 4.0352 307.26 0.1328

(3) 2.6687 464.59 0.0623 3.9834 311.25 0.2184

E-3-4

(1) 2.9963 413.78 0.0000 3.8219 324.41 0.8926

(2) 2.9988 413.44 0.0000 3.7716 328.74 0.8587

(3) 2.8854 429.69 0.0000 3.7982 326.43 0.9011

(4) 2.8883 429.26 0.0000 3.7494 330.68 0.8757

Z-3-4

(1) 2.8172 440.10 0.0026 4.0594 305.42 0.7033

(2) 2.7688 447.79 0.0616 4.0568 305.62 0.2901

(3) 2.8522 434.70 0.0026 4.0258 307.97 0.6132

(4) 2.7764 446.56 0.0557 4.0055 309.54 0.2118

E-3-5

(1) 2.9306 423.07 0.0000 3.6475 339.92 0.8355

(2) 2.8750 431.25 0.0000 3.7285 332.53 0.8385

(3) 2.7686 447.82 0.0000 3.7177 333.50 0.8635

(4) 2.8234 439.13 0.0000 3.6328 341.29 0.8423

33

Z-3-5

(1) 2.6727 463.89 0.0241 3.7034 334.78 0.0504

(2) 2.7932 443.88 0.0249 3.9088 317.19 0.0480

(3) 2.6865 461.50 0.0020 3.8437 322.56 0.6845

(4) 2.6644 465.33 0.0709 3.8792 319.61 0.2500

E-4-4

(1) 3.0362 408.35 0.0000 3.8308 323.65 0.9058

(2) 3.0339 408.66 0.0000 3.7789 328.09 0.8697

(3) 3.0360 408.37 0.0000 3.7283 332.55 0.8458

Z-4-4

(1) 2.8246 438.94 0.0685 4.1193 300.98 0.3452

(2) 2.8119 440.93 0.0666 4.0771 304.10 0.2790

(3) 2.8040 442.18 0.0661 4.0375 307.08 0.2458

E-4-5

(1) 2.9669 417.90 0.0000 3.6594 338.81 0.8592

(2) 2.9117 425.82 0.0000 3.7414 331.38 0.8773

(3) 2.9748 416.78 0.0000 3.6127 343.19 0.8266

(4) 2.9179 424.91 0.0000 3.6956 335.49 0.8507

Z-4-5

(1) 2.7796 446.06 0.0714 3.9325 315.28 0.3271

(2) 2.9672 417.85 0.0164 3.9647 312.72 0.0341

(3) 2.9678 417.76 0.0206 3.9815 311.40 0.0465

(4) 2.7769 446.49 0.0676 3.8981 318.06 0.2823

E-5-5

(1) 2.9094 426.15 0.0000 3.5058 353.65 0.8090

(2) 2.8446 435.85 0.0001 3.5751 346.80 0.8159

(3) 2.7949 443.61 0.0000 3.6666 338.14 0.8215

Z-5-5

(1) 2.7128 457.03 0.0382 3.7787 328.12 0.0484

(2) 2.5864 479.38 0.0597 3.8745 320.00 0.0193

(3) 2.6498 467.89 0.0800 3.7731 328.60 0.2922

Table S17. Free energies barriers (ΔG‡) of thermal Z→E isomerization pathways for azobispyrazoles in

solution (DMSO).

Conformation of

Z-isomers

Conformation of

transition states

ΔG‡soln

(kJ/mol)

Pathway

Proportion

Avg. ΔG‡soln

(kJ/mol)

Z-3-3

(1)

3-3 TS

(1) 125.75 25.68%

122.80 (2) (2) 127.28 4.40%

(4) 121.07 53.94%

(3) (3) 122.63 15.98%

Z-3-4 (1) 3-4 TS (1) 127.68 8.01%

129.18 (5) 128.47 5.82%

34

(2) (2) 129.18 12.79%

(6) 129.92 9.49%

(3) (3) 130.87 6.37%

(7) 128.24 18.41%

(4) (4) 128.93 33.33%

(8) 133.27 5.78%

Z-3-5

(1)

3-5 TS

(1) 117.64 9.13%

116.02

(5) 136.41 0.005%

(2) (2) 119.13 8.27%

(6) 138.69 0.003%

(3) (3) 116.31 62.81%

(7) 123.21 3.87%

(4) (4) 110.52 15.87%

(8) 125.00 0.05%

Z-4-4

(1)

4-4 TS

(1) 131.24 39.98%

132.34 (2) (2) 131.26 13.35%

(4) 131.19 13.76%

(3) (3) 134.61 32.91%

Z-4-5

(1)

4-5 TS

(1) 116.01 19.42%

121.65

(5) 124.08 0.75%

(2) (2) 125.27 22.18%

(6) 144.03 0.01%

(3) (3) 124.93 30.81%

(7) 145.19 0.01%

(4) (4) 118.61 25.83%

(8) 126.67 1.00%

Z-5-5

(1)

5-5 TS

(1) 126.65 1.93%

114.23 (2) (2) 121.28 16.82%

(4) 107.81 0.001%

(3) (3) 112.48 81.25%

35

Figure S22. Optimized geometries of ground-state conformations for symmetric azobispyrazoles.

36

Figure S23. Optimized geometries of ground-state conformations for asymmetric azobispyrazoles.

38

Figure S24. Optimized geometries of transition-state conformations for azobispyrazoles.

39

Figure S25. The frontier molecular orbitals (FMOs) and natural transition orbitals (NTOs) of 3-3 (isosurface

value of 0.05).

40


value of 0.05).

41


value of 0.05).

43


value of 0.05).

45


value of 0.05).

46


value of 0.05).

47

Figure S31. Potential energy curves of rotation and inversion thermal Z→E isomerization pathways by

relaxed scans (taking symmetric 3-3 and asymmetric 3-5 as examples).

48

Cartesian coordinates for optimized geometries (in acetonitrile)

E-3-3 (1)

N 0.29289800 -0.55792600 -0.02031800

N 3.67220400 0.21234300 0.01187300

N 2.41126700 0.63431600 0.01678400

C 1.68268000 -0.49251400 -0.01520000

C 2.50352400 -1.64045900 -0.03937200

H 2.18986800 -2.67348800 -0.06673300

C 3.78576200 -1.13772900 -0.02181700

H 4.75388600 -1.61735400 -0.02947000

C 4.75023600 1.17480300 0.04575000

H 4.68899800 1.82928400 -0.82664500

H 5.69781700 0.63660100 0.03377700

H 4.68117500 1.77534300 0.95559300

N -0.29289800 0.55792600 -0.02025200

N -3.67220400 -0.21234400 0.01187300

N -2.41126800 -0.63431900 0.01672800

C -1.68268000 0.49251400 -0.01513300

C -2.50352300 1.64046200 -0.03916900

H -2.18986600 2.67349500 -0.06641300

C -3.78576100 1.13773200 -0.02166300

H -4.75388500 1.61735800 -0.02925600

C -4.75023700 -1.17480600 0.04564400

H -4.68116800 -1.77545700 0.95541300

H -5.69781800 -0.63660200 0.03374400

H -4.68900900 -1.82918200 -0.82683100

E-3-3 (2)

N 0.33812400 -0.21533000 0.00000500

N 3.75148700 -0.35612000 0.00002600

N 2.54983000 -0.92203500 0.00002600

C 1.68956500 0.10516700 0.00000900

C 2.36458600 1.34920300 -0.00000100

H 1.93422000 2.33867200 -0.00001500

C 3.69473200 1.00075800 0.00001000

H 4.59718200 1.59578800 0.00000900

C 4.93735400 -1.18194800 0.00004200

H 4.95025600 -1.81285900 0.89176500

H 5.81252900 -0.53263600 0.00004200

H 4.95026800 -1.81287600 -0.89166900

N -0.41458800 0.79563000 -0.00001400

N -3.63429600 -0.48355800 -0.00000500

N -2.32336300 -0.70530800 0.00000700

C -1.77791000 0.52055600 -0.00001700

49

C -2.76587300 1.52838600 -0.00004500

H -2.61563500 2.59783900 -0.00006800

C -3.95509500 0.83310600 -0.00003700

H -4.98567200 1.15758300 -0.00005000

C -4.54913000 -1.60285000 0.00001400

H -4.38640800 -2.21263100 0.89158100

H -5.56906500 -1.21900900 0.00001600

H -4.38642000 -2.21265400 -0.89154100

E-3-3 (3)

N -0.44542000 -0.44575700 -0.00012300

N -3.84440200 -0.10735400 -0.00002400

N -2.73421500 -0.83658100 0.00076500

C -1.73859400 0.05975500 -0.00016400

C -2.23158600 1.38616900 -0.00142800

H -1.66544600 2.30472200 -0.00267000

C -3.59755700 1.22802200 -0.00124300

H -4.40742700 1.94407300 -0.00199500

C -5.13457200 -0.75859600 0.00290800

H -5.23244300 -1.39104800 -0.88235100

H -5.90994200 0.00726600 -0.00832800

H -5.23918000 -1.37163900 0.90107300

N 0.44542000 0.44575700 -0.00004700

N 3.84440100 0.10735500 -0.00020800

N 2.73421500 0.83658200 0.00080700

C 1.73859400 -0.05975500 -0.00026800

C 2.23158600 -1.38616800 -0.00185400

H 1.66544700 -2.30472200 -0.00327000

C 3.59755700 -1.22802100 -0.00171000

H 4.40742700 -1.94407200 -0.00266600

C 5.13457100 0.75859700 0.00283200

H 5.23927900 1.37131000 0.90121000

H 5.90994000 -0.00726100 -0.00877100

H 5.23234500 1.39137300 -0.88220600

Z-3-3 (1)

N 0.61009800 -2.14705600 -0.13955200

N 2.35292500 0.81261700 0.35658300

N 1.31661400 0.03009300 0.65594100

C 1.41218400 -0.99361800 -0.19901700

C 2.53837200 -0.86927800 -1.03899100

H 2.86583600 -1.54828800 -1.81227100

C 3.10534100 0.32874300 -0.65960300

H 3.97494800 0.86192900 -1.01608400

50

C 2.59072000 2.01006000 1.12974400

H 1.71484500 2.66068700 1.08176500

H 3.45412500 2.52711900 0.71179300

H 2.79120100 1.74724400 2.17127800

N -0.61004200 -2.14705700 0.13977100

N -2.35292200 0.81254900 -0.35658600

N -1.31655800 0.03005800 -0.65584000

C -1.41216300 -0.99364000 0.19913100

C -2.53842500 -0.86932100 1.03901000

H -2.86592900 -1.54832800 1.81227500

C -3.10540700 0.32867000 0.65954800

H -3.97506300 0.86183300 1.01594400

C -2.59069500 2.00996800 -1.12979100

H -2.79109700 1.74712300 -2.17133300

H -3.45414100 2.52701500 -0.71191100

H -1.71483900 2.66061700 -1.08176600

Z-3-3 (2)

N -0.58965800 1.84418000 -0.47517300

N -3.05267300 -0.44011500 0.08567900

N -2.54689800 0.65127000 -0.46717500

C -1.26061600 0.67988700 -0.07900100

C -0.96336700 -0.41985100 0.76791100

H -0.03602600 -0.67334700 1.25499200

C -2.14970800 -1.10862200 0.84790800

H -2.42204500 -2.01147500 1.37626600

C -4.42839000 -0.80725200 -0.16540400

H -5.08327100 0.02586600 0.09753100

H -4.67392400 -1.67394300 0.44793600

H -4.56161600 -1.05651300 -1.22086300

N 0.64636400 2.02640900 -0.38543300

N 2.63572400 -0.80923900 -0.20938300

N 1.59323800 -0.15409100 -0.73051200

C 1.55068500 0.99678200 -0.05472000

C 2.59047700 1.09114400 0.89091000

H 2.79960400 1.90342200 1.57102000

C 3.25589400 -0.11244400 0.76872700

H 4.11360100 -0.51646700 1.28753900

C 3.01683400 -2.09297200 -0.75151700

H 3.37876700 -1.97728000 -1.77644500

H 3.80949300 -2.51076400 -0.13076300

H 2.15540200 -2.76387400 -0.74461500

Z-3-3 (3)

51

N 0.62671600 1.76240400 0.00930200

N 3.31932600 -0.34068000 0.02894700

N 2.69147200 0.77912700 -0.31005200

C 1.43426900 0.62257500 0.13307400

C 1.28271800 -0.61607600 0.80495700

H 0.40995900 -1.01682900 1.29491500

C 2.52488800 -1.20016700 0.71261500

H 2.90307700 -2.14522000 1.07610400

C 4.69643100 -0.54209900 -0.36018500

H 4.76574200 -0.68733500 -1.44136000

H 5.07658900 -1.42655700 0.15079300

H 5.28632500 0.33001900 -0.07202000

N -0.62671600 1.76240400 -0.00930700

N -3.31932600 -0.34068100 -0.02894700

N -2.69147200 0.77912800 0.31004900

C -1.43426900 0.62257500 -0.13307700

C -1.28271800 -0.61607800 -0.80495700

H -0.40995900 -1.01683200 -1.29491400

C -2.52488800 -1.20016900 -0.71261400

H -2.90307700 -2.14522300 -1.07610100

C -4.69643100 -0.54209900 0.36018500

H -5.28632500 0.33001800 0.07201800

H -5.07658900 -1.42655800 -0.15079200

H -4.76574200 -0.68733300 1.44136000

E-3-4 (1)

N -3.87202700 -0.13587100 -0.00005600

N 0.40910900 0.49385900 -0.00004300

C -1.76745000 0.06475000 -0.00003700

C 1.71225600 0.03266600 0.00000400

C 2.26004500 -1.27587200 0.00006700

H 1.73771700 -2.22273100 0.00009100

C -2.28326400 1.38257400 -0.00021100

H -1.73326600 2.31090500 -0.00034400

C -3.64704600 1.20201100 -0.00021300

H -4.46827600 1.90509500 -0.00032000

N -0.46400700 -0.41817200 0.00002100

C -5.14952100 -0.80985700 0.00017200

H -5.93930900 -0.05866000 -0.00070000

H -5.24016200 -1.43545700 -0.89093200

H -5.24070800 -1.43396200 0.89227600

N -2.74784700 -0.84718200 0.00006400

C 2.82217800 0.87423300 -0.00001300

H 2.89637700 1.95226600 -0.00005500

N 3.58232700 -1.23265700 0.00008700

52

N 3.90029600 0.08043400 0.00003900

C 5.28946600 0.47452400 0.00006400

H 5.78479100 0.08335900 0.89169500

H 5.78486500 0.08319100 -0.89145200

H 5.34302300 1.56294900 -0.00003700

E-3-4 (2)

N 3.79427300 -0.35064800 -0.00003700

N -0.38474800 0.77509100 0.00003100

C 1.72780900 0.09574100 -0.00000700

C -1.73429200 0.47442700 0.00003000

C -2.76193900 1.44402800 0.00006600

H -2.65787300 2.52152500 0.00009900

C 2.39477800 1.34394900 0.00002400

H 1.95841200 2.33083000 0.00005700

C 3.72784200 1.00443600 0.00000400

H 4.62580100 1.60632000 0.00001400

N 0.37706800 -0.23162400 -0.00000700

C 4.98421400 -1.16923500 -0.00007800

H 5.85609000 -0.51541500 -0.00004000

H 5.00161100 -1.80047800 0.89150100

H 5.00161700 -1.80038100 -0.89172600

N 2.59446800 -0.92510800 -0.00004500

C -2.40973500 -0.74909100 -0.00000900

H -2.05113800 -1.76746300 -0.00004500

N -3.95868000 0.87556200 0.00005100

N -3.71428100 -0.45245600 0.00000400

C -4.82573800 -1.37532300 -0.00000100

H -5.43639700 -1.21579000 0.89155400

H -5.43654700 -1.21558500 -0.89141600

H -4.43591000 -2.39287700 -0.00015100

E-3-4 (3)

N -3.67873500 -0.45891000 -0.00000200

N 0.30197400 -0.26211300 0.00000000

C -1.80231100 0.51123300 -0.00000100

C 1.65632800 0.01833300 0.00000000

C 2.37731500 1.24028000 0.00000100

H 1.98914200 2.24953900 0.00000100

C -2.77263700 1.53624200 0.00000000

H -2.60365700 2.60294300 0.00000100

C -3.97478600 0.86258500 -0.00000100

H -4.99921000 1.20622500 -0.00000100

N -0.43311300 0.76470000 0.00000000

53

C -4.61273600 -1.56159000 -0.00000300

H -5.62586100 -1.15991400 -0.00000300

H -4.46186500 -2.17479200 -0.89145600

H -4.46186600 -2.17479300 0.89144800

N -2.36984100 -0.70398600 -0.00000200

C 2.64179200 -0.96631000 0.00000000

H 2.56775700 -2.04437900 0.00000000

N 3.68151500 1.01790000 0.00000100

N 3.81832500 -0.32636500 0.00000100

C 5.14229000 -0.90386400 0.00000100

H 5.68564100 -0.58260600 -0.89161400

H 5.68564100 -0.58260600 0.89161500

H 5.05022900 -1.98967900 0.00000100

E-3-4 (4)

N -3.70710300 -0.22706700 -0.00002600

N 0.26746700 -0.53451100 0.00001000

C -1.72293400 0.49735500 -0.00001500

C 1.64710200 -0.43526400 0.00001800

C 2.52049700 -1.54612300 0.00003500

H 2.25852200 -2.59643100 0.00004400

C -2.55539200 1.63714000 -0.00003000

H -2.25264900 2.67381600 -0.00003500

C -3.83312000 1.12137000 -0.00003600

H -4.80566600 1.59220800 -0.00004800

N -0.33274800 0.57631500 -0.00000500

C -4.77441500 -1.20138500 -0.00002100

H -5.72796000 -0.67354100 -0.00006600

H -4.70329900 -1.82888700 -0.89142500

H -4.70335000 -1.82882700 0.89142900

N -2.43991900 -0.63643400 -0.00001200

C 2.49635000 0.67491700 0.00001100

H 2.29229000 1.73515100 -0.00000200

N 3.78834700 -1.16099300 0.00003800

N 3.74298800 0.18867200 0.00002400

C 4.97887800 0.93737000 0.00002200

H 5.55926900 0.68915700 0.89155100

H 5.55927600 0.68914300 -0.89149800

H 4.74325000 2.00129600 0.00001200

Z-3-4 (1)

N 2.82496000 0.84394000 -0.00007300

N -0.54995400 -1.79328000 -0.00049500

C 1.69016600 -0.94684800 -0.00023500

54

C -1.33319300 -0.64701300 -0.00026100

C -1.22304500 0.77860600 0.00002800

H -0.32665400 1.37600800 0.00009200

C 3.05339400 -1.33258100 0.00000900

H 3.44366700 -2.33949800 0.00008900

C 3.74935200 -0.14746800 0.00011900

H 4.80653700 0.07602300 0.00030800

N 0.70350700 -1.92999100 -0.00046300

C 3.06904200 2.26852700 -0.00005700

H 4.14582700 2.43656600 0.00004300

H 2.62801300 2.71953000 -0.89198200

H 2.62784600 2.71954600 0.89177900

N 1.57565300 0.39030400 -0.00028500

C -2.71928700 -0.86293600 -0.00024900

H -3.27637800 -1.78908000 -0.00041100

N -2.41666800 1.34692500 0.00020000

N -3.30906400 0.32952300 0.00003200

C -4.72296800 0.62461500 0.00014600

H -4.97800900 1.20188400 0.89173700

H -4.97811100 1.20212000 -0.89126400

H -5.27657000 -0.31398900 0.00005400

Z-3-4 (2)

N 3.29318400 -0.38039100 -0.02871600

N -0.59010900 1.81578000 0.03011600

C 1.46107400 0.66886800 0.15839500

C -1.40483800 0.68739400 -0.06243200

C -1.27621200 -0.63409500 -0.57653800

H -0.40130200 -1.13659700 -0.96142100

C 1.33086800 -0.49756400 0.95087400

H 0.49377600 -0.81241100 1.55416600

C 2.53852400 -1.14144300 0.79811500

H 2.91612400 -2.06652300 1.21046800

N 0.66566900 1.82079900 0.03563900

C 4.62163400 -0.66726800 -0.51794800

H 5.00343900 -1.54404300 0.00502600

H 4.59358700 -0.86750700 -1.59215900

H 5.27462800 0.18634000 -0.32506800

N 2.67235200 0.73461900 -0.41013700

C -2.76549500 0.80192900 0.22748500

H -3.32960100 1.63265700 0.62718800

N -2.44411600 -1.25501400 -0.58206200

N -3.32939200 -0.37101700 -0.07348100

C -4.70934500 -0.76284700 0.09615800

H -5.10903500 -1.11244600 -0.85798600

55

H -4.78137700 -1.56399000 0.83579000

H -5.27789800 0.10199100 0.43708600

Z-3-4 (3)

N 2.55829400 0.94051000 -0.00012100

N -0.50865400 -2.04344600 0.00003400

C 1.62723500 -0.96517700 -0.00005800

C -1.40582600 -0.98731900 0.00006200

C -2.78919800 -1.32239400 0.00013400

H -3.21164700 -2.31943800 0.00017000

C 3.02492400 -1.19799300 -0.00009200

H 3.52383600 -2.15569000 -0.00008700

C 3.58620600 0.05634200 -0.00013100

H 4.61249400 0.39419300 -0.00016500

N 0.75324700 -2.04808900 -0.00001600

C 2.64292000 2.38347000 -0.00015300

H 3.69429500 2.66951900 -0.00018900

H 2.15476400 2.78280100 -0.89219100

H 2.15481400 2.78283900 0.89189400

N 1.36689700 0.35236600 -0.00007700

C -1.41335500 0.41931700 0.00004000

H -0.60768100 1.13299800 -0.00001300

N -3.56075200 -0.25363300 0.00015600

N -2.69726700 0.78893000 0.00009700

C -3.21818400 2.13663400 0.00009900

H -3.82939400 2.29523400 -0.89137200

H -3.82931100 2.29526400 0.89162200

H -2.38124900 2.83458100 0.00004900

Z-3-4 (4)

N -3.07573700 0.44438800 -0.04190600

N 0.62977600 -2.02196600 -0.13828000

C -1.35501600 -0.78403800 0.09876200

C 1.51023500 -0.94695300 -0.03664000

C 2.88739300 -1.18273300 0.19925700

H 3.35998600 -2.13128700 0.42082200

C -1.22346600 0.19532900 1.11211300

H -0.43075600 0.31403600 1.83458900

C -2.35906500 0.96408300 0.98133000

H -2.70939900 1.82678500 1.53047800

N -0.62397900 -1.95662300 -0.16631400

C -4.32287800 0.93598000 -0.57979700

H -4.66364200 1.76701400 0.03770700

H -4.17938200 1.28054700 -1.60701700

56

H -5.06994500 0.13927800 -0.56583500

N -2.50069300 -0.63335400 -0.57679200

C 1.44299300 0.43204500 -0.27859200

H 0.62780600 1.09092800 -0.53149300

N 3.59382600 -0.06716500 0.13520900

N 2.69412100 0.89252500 -0.17046500

C 3.14396300 2.25469200 -0.34701000

H 3.60674900 2.61084700 0.57604200

H 3.87292600 2.29820000 -1.15936600

H 2.28419800 2.87818100 -0.59072500

E-3-5 (1)

N 0.66593000 0.25668400 0.00164600

N -3.64005900 -0.13585900 -0.00503300

N -0.26075600 -0.60018200 0.00003700

N -2.55932100 -0.90532500 -0.00346600

N 3.00326500 0.55637700 0.00023400

N 4.15792300 -0.10241000 -0.00085200

C -1.97392500 1.29843900 0.00371500

H -1.37604600 2.19677200 0.00581400

C 3.82627100 -1.40194700 -0.00084800

H 4.60635500 -2.15234700 -0.00146100

C -3.34412400 1.19029100 0.00011000

H -4.12719100 1.93551800 -0.00010900

C 2.99217800 2.00173200 -0.00064000

H 3.50608300 2.37319500 0.88868800

H 1.95669600 2.33849600 0.00460400

H 3.49663800 2.37248000 -0.89571000

C 2.44387100 -1.58412300 0.00007900

H 1.87614600 -2.50217500 0.00044300

C 1.93254400 -0.28655500 0.00071200

C -1.53031600 -0.04588100 0.00099700

C -4.95459100 -0.73714200 0.00179600

H -5.10270500 -1.29973900 0.92668600

H -5.69907300 0.05574600 -0.06651000

H -5.05553900 -1.40909700 -0.85309000

E-3-5 (2)

N -0.68835200 -0.80297600 -0.00003400

N 3.52432000 0.16917800 0.00000600

N 0.11157700 0.17432500 -0.00000500

N 2.34930700 0.78695400 0.00002000

N -2.62970500 0.74124200 0.00000900

N -3.95978900 0.63421700 0.00000600

57

C 2.06498300 -1.47513300 -0.00005100

H 1.59191800 -2.44491700 -0.00008200

C -4.22761600 -0.67577000 -0.00003000

H -5.25579700 -1.01252200 -0.00003900

C 3.40866500 -1.18434100 -0.00003700

H 4.28447400 -1.81792000 -0.00005300

C -2.03601500 2.06186900 0.00004400

H -2.86131600 2.77396500 0.00006700

H -1.41622800 2.20467700 -0.88690000

H -1.41622100 2.20462700 0.88699100

C -3.05582100 -1.43210500 -0.00005100

H -2.93271600 -2.50535700 -0.00008000

C -2.03027200 -0.48990800 -0.00002500

C 1.44551100 -0.20271900 -0.00001400

C 4.74558900 0.94241000 0.00002600

H 4.78513600 1.57211200 0.89176600

H 5.59205700 0.25612600 0.00006100

H 4.78518800 1.57208500 -0.89173000

E-3-5 (3)

N 0.53258400 -0.62398800 0.00028700

N -3.43680400 -0.33920100 -0.00177400

N -0.07429000 0.48362000 0.00092600

N -2.16999300 -0.74081300 -0.00057600

N 2.72077100 0.54869900 -0.00001200

N 4.01001200 0.20418300 -0.00003500

C -2.29873500 1.53378900 0.00056000

H -2.00172100 2.57207100 0.00078700

C 4.03793400 -1.13258900 0.00034700

H 4.98876300 -1.64885000 0.00043100

C -3.57222900 1.00971800 -0.00085300

H -4.54807700 1.47342200 -0.00157500

C 2.37568600 1.95484700 -0.00065600

H 3.31594200 2.50630400 -0.00154700

H 1.79275400 2.20811000 0.88653500

H 1.79174300 2.20699800 -0.88750100

C 2.74922900 -1.66574700 0.00053500

H 2.43536000 -2.69941200 0.00081400

C 1.90923900 -0.55475300 0.00032700

C -1.46009000 0.39835100 0.00059200

C -4.49945400 -1.31948900 0.00099700

H -4.43763200 -1.92958800 0.90502100

H -5.45533500 -0.79674400 -0.02331000

H -4.40985800 -1.96196800 -0.87765300

58

E-3-5 (4)

N -0.56903300 0.06670800 0.00001300

N 3.39181600 0.38108600 -0.00005400

N 0.19342100 -0.93902300 -0.00012800

N 2.07938600 0.58559400 0.00006600

N -2.81575900 0.76913200 0.00015100

N -4.06841700 0.32489900 0.00022100

C 2.55190400 -1.64329800 -0.00042900

H 2.41595200 -2.71461400 -0.00064100

C -3.97128600 -1.01303100 0.00020200

H -4.87147500 -1.61399000 0.00025700

C 3.73092200 -0.93177900 -0.00035600

H 4.76586700 -1.24188200 -0.00048300

C -2.54679100 2.18924800 0.00011800

H -2.98151800 2.64527000 -0.89211600

H -1.46745500 2.33421200 0.00016700

H -2.98161300 2.64531900 0.89227900

C -2.64281200 -1.43641000 0.00011200

H -2.24679400 -2.44057300 0.00008500

C -1.91022000 -0.24936900 0.00007800

C 1.55046600 -0.64835600 -0.00016100

C 4.29207100 1.51248600 0.00013300

H 4.12057900 2.11945500 0.89189900

H 5.31688800 1.14215400 0.00013600

H 4.12067000 2.11969400 -0.89148900

Z-3-5 (1)

N -0.97600700 -1.88994700 -0.33629200

N 2.17547400 0.85929800 -0.17644400

N 0.26121500 -2.03806900 -0.18131100

N 0.97345400 0.31117400 -0.24619500

N -1.73930300 0.17006600 0.73871600

N -2.51132100 1.23803900 0.48247700

C 2.57346900 -1.28333900 0.04685100

H 3.03879700 -2.25012700 0.16868000

C -2.88419800 1.10265000 -0.78863300

H -3.52187900 1.84893000 -1.24553300

C 3.17195800 -0.04645000 0.00150900

H 4.20329800 0.26583300 0.07705100

C -1.13971000 0.01299300 2.04014300

H -0.21875500 0.59915000 2.10851700

H -0.91205500 -1.04017600 2.21152200

H -1.85149500 0.35285100 2.79339500

C -2.37539000 -0.07347700 -1.36034200

59

H -2.51298500 -0.46232600 -2.35846200

C -1.61274300 -0.63303200 -0.34688000

C 1.19623900 -1.00861300 -0.11262500

C 2.31130600 2.29594500 -0.28333000

H 1.74234000 2.77661200 0.51530100

H 3.36583900 2.55331200 -0.19148300

H 1.93296600 2.62855500 -1.25214400

Z-3-5 (2)

N 1.01346400 1.83779800 -0.08092800

N -2.89899600 -0.30404200 -0.13461100

N -0.23756700 1.80056600 0.01550100

N -2.31486700 0.85181300 0.11664800

N 1.92847600 -0.27084800 0.73186300

N 2.77518900 -1.24442100 0.35899000

C -0.77864700 -0.68496800 -0.57324300

H 0.13960500 -1.16424400 -0.87257700

C 3.16989500 -0.91334300 -0.86904800

H 3.86520100 -1.55009400 -1.40126100

C -2.02765400 -1.25694000 -0.55707300

H -2.36444400 -2.25224200 -0.81002200

C 1.31246300 -0.31490700 2.03725200

H 0.45603400 -0.99526000 2.03681600

H 0.97994000 0.68575000 2.31572500

H 2.05400200 -0.66002500 2.75882300

C 2.59698800 0.29577200 -1.29531800

H 2.72601400 0.81967400 -2.23078300

C 1.78112300 0.66668500 -0.23944100

C -1.00818200 0.64937500 -0.13734300

C -4.32137200 -0.45927500 0.08193700

H -4.84981300 0.36615000 -0.39739200

H -4.63877000 -1.40452200 -0.35731800

H -4.53780500 -0.46059900 1.15296900

Z-3-5 (3)

N -0.96398300 -1.33645100 0.00000500

N 2.87884400 0.54546600 0.00000500

N 0.23573300 -1.72452700 0.00000600

N 1.56574100 0.36347000 0.00000300

N -2.86825800 -0.06832300 0.00000600

N -3.38592700 1.14770200 -0.00000700

C 2.65408100 -1.63154900 0.00000700

H 2.82661800 -2.69751400 0.00000800

C -2.33681600 1.98323100 -0.00003000

60

H -2.50290300 3.05271900 -0.00004500

C 3.57965100 -0.61698200 0.00000700

H 4.66013900 -0.61623700 0.00000900

C -3.73584600 -1.22711400 0.00003400

H -3.56237400 -1.83559300 0.88957400

H -3.56236800 -1.83563900 -0.88947200

H -4.76008500 -0.85627300 0.00002200

C -1.12708900 1.29425200 -0.00002900

H -0.12474500 1.68341300 -0.00004300

C -1.49175200 -0.06165800 -0.00000500

C 1.40009500 -0.97052900 0.00000400

C 3.41357300 1.88913300 0.00000400

H 3.07437600 2.42025600 0.89217200

H 4.50148900 1.82989700 0.00001100

H 3.07438600 2.42025100 -0.89217000

Z-3-5 (4)

N 0.92200500 -1.33581100 -0.38032700

N -3.28783500 0.10342100 0.08093200

N -0.32184400 -1.50444700 -0.38100000

N -2.52017100 -0.84451800 -0.43460500

N 2.89384200 -0.18892500 0.12791300

N 3.50966600 0.98582600 0.04540800

C -1.26909500 0.62088700 0.77649300

H -0.44034900 1.10226500 1.26922500

C 2.59689900 1.82851000 -0.45393000

H 2.86402200 2.85976200 -0.64506200

C -2.59065400 0.99602900 0.82778500

H -3.08575900 1.81515200 1.32984600

C 3.58002400 -1.33905600 0.66945000

H 4.63728200 -1.25231500 0.41916300

H 3.15872500 -2.24033200 0.22284500

H 3.46156400 -1.38624600 1.75572200

C 1.36800100 1.20022400 -0.65922200

H 0.46151900 1.62523200 -1.06026800

C 1.58448400 -0.12036000 -0.25728100

C -1.27126900 -0.53863100 -0.04088000

C -4.70643900 0.11615600 -0.19766700

H -5.13169900 -0.86124900 0.03781900

H -5.17513100 0.87958500 0.42291700

H -4.87920900 0.34477500 -1.25223000

E-4-4 (1)

N 0.42746500 0.46562500 0.00000200

61

N 3.63306500 -1.20891900 0.00000400

C 1.74098400 0.02566100 0.00000300

C 2.83674400 0.88422000 0.00001000

H 2.89428900 1.96328000 0.00001300

N -0.42746500 -0.46562500 -0.00000200

N -3.92938100 -0.10747700 -0.00001400

C -1.74098400 -0.02566100 -0.00000200

C -2.31031100 1.27292600 0.00000100

H -1.80405900 2.22848900 0.00000200

C -2.83674400 -0.88422000 -0.00001000

H -2.89428900 -1.96328000 -0.00001400

N -3.63306500 1.20891900 -0.00000400

C -5.31125200 -0.52572500 0.00001400

H -5.81427400 -0.14375400 -0.89140200

H -5.34592100 -1.61496200 -0.00016200

H -5.81416900 -0.14404400 0.89161400

C 2.31031100 -1.27292600 0.00000000

H 1.80405900 -2.22848900 -0.00000200

N 3.92938100 0.10747700 0.00001300

C 5.31125200 0.52572500 -0.00001400

H 5.34592100 1.61496200 0.00016000

H 5.81427300 0.14375500 0.89140200

H 5.81417000 0.14404200 -0.89161300

E-4-4 (2)

N -0.40326100 0.74379500 0.00004400

N -3.97902400 0.90277100 0.00006300

C -1.76031500 0.46386300 0.00003900

C -2.45679200 -0.74673300 -0.00000400

H -2.11631900 -1.77126200 -0.00004400

N 0.34054300 -0.27831600 0.00000300

N 3.86099500 -0.31953500 -0.00001500

C 1.69564600 0.00956700 0.00000800

C 2.40837600 1.23544200 0.00004700

H 2.01359500 2.24215700 0.00008400

C 2.68709900 -0.96778700 -0.00003200

H 2.62120800 -2.04637200 -0.00007000

N 3.71530100 1.02207500 0.00003300

C 5.18810000 -0.88951000 -0.00004100

H 5.10229100 -1.97587100 -0.00008800

H 5.73025900 -0.56584500 -0.89158100

H 5.73026100 -0.56592300 0.89152600

C -2.77112600 1.45028900 0.00007900

H -2.64872500 2.52587300 0.00011800

N -3.75824500 -0.42775500 0.00001100

62

C -4.88510800 -1.33214800 -0.00001100

H -5.49358000 -1.16299200 -0.89136900

H -4.51232800 -2.35613400 -0.00010500

H -5.49351000 -1.16313100 0.89142200

E-4-4 (3)

N 0.30674100 0.55260300 0.00000400

N 3.83664200 1.14571200 0.00001100

C 1.68771300 0.44048300 0.00000400

C 2.52615600 -0.67658500 -0.00000100

H 2.31281100 -1.73496300 -0.00000800

N -0.30674100 -0.55260300 -0.00000400

N -3.77908900 0.20180200 -0.00000300

C -1.68771300 -0.44048300 -0.00000400

C -2.57119300 -1.54248100 -0.00001200

H -2.31941300 -2.59531600 -0.00001800

C -2.52615600 0.67658500 0.00000100

H -2.31281100 1.73496300 0.00000800

N -3.83664200 -1.14571200 -0.00001100

C -5.00711800 0.96314800 0.00000100

H -5.59056600 0.72175500 0.89147900

H -4.76042200 2.02459500 0.00000500

H -5.59056700 0.72176200 -0.89147900

C 2.57119300 1.54248100 0.00001200

H 2.31941300 2.59531600 0.00001800

N 3.77908900 -0.20180200 0.00000300

C 5.00711800 -0.96314800 -0.00000100

H 4.76042200 -2.02459500 -0.00000500

H 5.59056600 -0.72175500 -0.89147900

H 5.59056700 -0.72176200 0.89147900

Z-4-4 (1)

N -0.62855600 1.87707300 -0.00390700

N -2.44407100 -1.19469700 0.70525100

C -1.42960700 0.73336100 0.09003800

C -2.75516200 0.75627800 -0.33916100

H -3.30859000 1.51392000 -0.87549300

N 0.62855600 1.87707300 0.00390600

N 3.30341500 -0.41020400 -0.02534100

C 1.42960700 0.73336100 -0.09003800

C 1.30479800 -0.52016800 -0.74833200

H 0.45430700 -0.93522100 -1.26973500

C 2.75516300 0.75627800 0.33916100

H 3.30859100 1.51392000 0.87549200

63

N 2.44407100 -1.19469700 -0.70525100

C 4.63998700 -0.88494000 0.24738400

H 5.20959600 -0.07846800 0.70869200

H 4.60316300 -1.74094700 0.92587600

H 5.11883400 -1.18345800 -0.68749900

C -1.30479700 -0.52016800 0.74833200

H -0.45430700 -0.93522100 1.26973500

N -3.30341500 -0.41020400 0.02534100

C -4.63998700 -0.88494000 -0.24738400

H -5.11883300 -1.18345800 0.68749900

H -5.20959600 -0.07846800 -0.70869200

H -4.60316300 -1.74094800 -0.92587600

Z-4-4 (2)

N 0.57579300 -1.97598300 -0.25420900

N 2.30634200 1.00167400 0.91468000

C 1.33023100 -0.82265100 -0.00364900

C 2.60354300 -0.66393500 -0.54573400

H 3.13552200 -1.25195800 -1.28002700

N -0.67760000 -2.04067400 -0.18488100

N -2.71233900 0.89621800 -0.17246000

C -1.54033100 -0.95164500 -0.03263700

C -2.88071600 -1.14016400 0.38138900

H -3.33586700 -2.05708900 0.73371100

C -1.48666400 0.39952500 -0.39115100

H -0.70059100 1.01581400 -0.79858400

N -3.57681000 -0.01573200 0.31492400

C -3.16213600 2.25014500 -0.40259700

H -3.47954500 2.69937700 0.54131200

H -2.33767000 2.82593100 -0.82235200

H -4.00097400 2.24496700 -1.10220000

C 1.21237200 0.25391100 0.91561700

H 0.40160900 0.48743300 1.59088800

N 3.12831300 0.43785400 0.00880400

C 4.39952900 1.05774600 -0.28467000

H 4.93332400 1.24734300 0.64858900

H 4.98347200 0.38131300 -0.90860600

H 4.24611000 2.00204400 -0.81353900

Z-4-4 (3)

N 0.62171000 -2.12031600 -0.09132600

N 3.40923100 0.07326700 -0.51243100

C 1.44292900 -0.98920400 -0.12492200

C 1.41364200 0.26273600 0.49747900

64

H 0.67551300 0.75687900 1.10996700

N -0.62180500 -2.12028600 0.09115600

N -2.59672100 0.83977900 -0.24071900

C -1.44296400 -0.98913600 0.12482800

C -2.72703900 -1.04285900 0.71827900

H -3.14946800 -1.85558000 1.29541100

C -1.41357300 0.26289000 -0.49740000

H -0.67537600 0.75708300 -1.10976500

N -3.40924300 0.07337800 0.51234300

C -3.05513600 2.13403900 -0.69154000

H -2.24879300 2.61846500 -1.24165700

H -3.92441600 2.01433900 -1.34249100

H -3.32898300 2.74565200 0.17085100

C 2.72696000 -1.04291000 -0.71846800

H 3.14931000 -1.85557500 -1.29573900

N 2.59680100 0.83960400 0.24079400

C 3.05530100 2.13379000 0.69174000

H 3.32895700 2.74556200 -0.17059900

H 2.24907300 2.61811000 1.24212000

H 3.92472200 2.01397900 1.34248000

E-4-5 (1)

N -0.68588800 0.23784400 -0.00000200

N -3.01837300 0.58136300 -0.00000400

N -4.18840100 -0.05486700 -0.00000300

C -1.96462700 -0.28110700 -0.00000100

C -2.50143200 -1.56796700 -0.00000100

H -1.95228400 -2.49723900 -0.00000300

C -2.97889300 2.02542200 0.00001000

H -1.93687300 2.34180700 -0.00008800

H -3.48015400 2.40784900 0.89210600

H -3.48032800 2.40786100 -0.89198300

C -3.88103700 -1.35900800 -0.00000200

H -4.67488400 -2.09509300 -0.00000400

N 0.22093800 -0.64370300 0.00000400

N 3.69149800 -0.11899900 -0.00000100

C 1.50366200 -0.13939400 0.00000100

C 2.00970900 1.18698800 -0.00000700

H 1.45842400 2.11730700 -0.00001200

C 2.64069000 -0.94610800 0.00000500

H 2.74823000 -2.02129900 0.00001100

N 3.33161800 1.18470600 -0.00000800

C 5.09308400 -0.46755000 0.00000400

H 5.57454600 -0.05978800 0.89168700

H 5.18208100 -1.55373000 -0.00002800

65

H 5.57456200 -0.05973500 -0.89164700

E-4-5 (2)

N -0.70192000 -0.78070700 0.00005700

N -2.67716200 0.72337900 -0.00006600

N -4.00724100 0.58929500 -0.00007700

C -2.05168800 -0.49410400 0.00002000

C -3.05740700 -1.45696600 0.00006600

H -2.91209700 -2.52747000 0.00013400

C -2.11338700 2.05669900 -0.00014500

H -1.49735900 2.21472000 -0.88718800

H -1.49742300 2.21485300 0.88692000

H -2.95462400 2.75004600 -0.00022600

C -4.24579300 -0.72524400 0.00000300

H -5.26643300 -1.08467600 0.00001200

N 0.07699000 0.21649400 0.00002300

N 3.58910500 0.14971200 0.00008000

C 1.41678400 -0.11416900 0.00005800

C 2.09075400 -1.36303200 0.00012200

H 1.66525800 -2.35713500 0.00015800

C 2.43865400 0.83359700 0.00003300

H 2.40560300 1.91375600 -0.00001500

N 3.40171400 -1.18907500 0.00013500

C 4.93443100 0.67603000 0.00007700

H 5.46447100 0.33346500 -0.89153200

H 4.88413600 1.76449500 0.00002700

H 5.46444400 0.33354500 0.89173300

E-4-5 (3)

N -0.60911200 0.09393600 -0.00000600

N -2.86954700 0.76293000 0.00002800

N -4.11760500 0.29840100 0.00002900

C -1.94805900 -0.23997600 -0.00000200

C -2.66131600 -1.43818300 -0.00002200

H -2.24920100 -2.43584300 -0.00004700

C -2.62630000 2.18717300 0.00005600

H -3.06883400 2.63632400 -0.89196400

H -1.54994100 2.35270000 0.00005600

H -3.06883000 2.63628800 0.89209600

C -3.99759900 -1.03627000 -0.00000100

H -4.88734300 -1.65284300 -0.00000600

N 0.16602600 -0.90526700 -0.00003800

N 3.48010400 0.35219100 -0.00002900

C 1.50870800 -0.59162800 -0.00004000

66

C 2.54504800 -1.55361900 -0.00007600

H 2.44932500 -2.63179600 -0.00010700

C 2.17443200 0.63872200 -0.00001000

H 1.80816800 1.65442400 0.00002300

N 3.73570400 -0.97510700 -0.00006900

C 4.58545700 1.28315600 -0.00000700

H 4.18843000 2.29785300 0.00002100

H 5.19679500 1.12667700 0.89151400

H 5.19678900 1.12672400 -0.89154100

E-4-5 (4)

N 0.57542200 -0.64153400 0.00000200

N 2.74952500 0.55703300 0.00000000

N 4.04557300 0.22966500 0.00000100

C 1.95260800 -0.55587900 0.00000200

C 2.80660700 -1.65561900 0.00000500

H 2.50655500 -2.69340800 0.00000800

C 2.38695800 1.95858000 -0.00000400

H 1.80064200 2.20514600 0.88693300

H 1.80064400 2.20514200 -0.88694300

H 3.32036000 2.52164700 -0.00000400

C 4.08923000 -1.10565900 0.00000500

H 5.04620200 -1.61073100 0.00000600

N -0.04836500 0.45923000 -0.00000200

N -3.50829400 -0.31648800 -0.00000200

C -1.42308700 0.33886500 -0.00000200

C -2.31267800 1.43745200 -0.00000500

H -2.06587500 2.49139900 -0.00000800

C -2.25547700 -0.78464600 0.00000000

H -2.03606300 -1.84183900 0.00000300

N -3.57365600 1.03301700 -0.00000500

C -4.73359600 -1.08264700 0.00000000

H -5.31699500 -0.84205700 -0.89159000

H -4.48278800 -2.14302900 0.00000200

H -5.31699500 -0.84205300 0.89158900

Z-4-5 (1)

N 0.96943200 -1.35745700 -0.46176100

N 2.88447100 -0.17221000 0.19346600

N 3.48670200 1.01509800 0.14110900

C 1.61048300 -0.13324500 -0.29315700

C 1.40191200 1.17579600 -0.73094300

H 0.52299400 1.57592300 -1.21223200

C 3.54464500 -1.30300500 0.80228600

67

H 4.61457100 -1.21774800 0.61154900

H 3.15386900 -2.21737900 0.35398700

H 3.36431900 -1.32536300 1.88094700

C 2.60089800 1.83149000 -0.43929100

H 2.86253200 2.86522900 -0.62531500

N -0.27633900 -1.52827900 -0.48056100

N -3.30619700 0.11039700 0.12121200

C -1.24000600 -0.58761600 -0.14207000

C -1.29459100 0.62901600 0.59909200

H -0.49196500 1.20157200 1.03874400

C -2.58187800 -0.87641900 -0.40765600

H -3.02746900 -1.70859400 -0.93390100

N -2.54390800 1.03110900 0.75313300

C -4.73968000 0.28605200 0.07604700

H -5.18269800 -0.58154200 -0.41228400

H -5.12755100 0.37445100 1.09294500

H -4.98500300 1.18973800 -0.48680700

Z-4-5 (2)

N 1.13804700 -1.85137100 -0.47538200

N 1.79957100 0.14788000 0.73855500

N 2.39275900 1.33818400 0.54491600

C 1.68336300 -0.55275900 -0.41857800

C 2.25319400 0.21446700 -1.42075300

H 2.33462600 -0.04051100 -2.46697800

C 1.36381400 -0.23622000 2.06054900

H 2.13605500 0.04268800 2.77874200

H 1.21773000 -1.31653800 2.09048800

H 0.42564000 0.26383200 2.31834600

C 2.66029800 1.38515800 -0.75886400

H 3.14788900 2.25644800 -1.17759600

N -0.10062900 -2.02708300 -0.32825800

N -2.29527000 0.77166700 -0.08968600

C -1.03496200 -1.01607300 -0.18605900

C -2.40188500 -1.34163900 0.00759800

H -2.82979000 -2.33141100 0.10262200

C -1.02614200 0.39078200 -0.24232200

H -0.24712500 1.12421700 -0.38299600

N -3.15571300 -0.26140200 0.06960700

C -2.80815900 2.12343500 -0.08324500

H -3.31497100 2.31512800 0.86485500

H -1.97405000 2.81424800 -0.20234400

H -3.51467400 2.25003200 -0.90641200

68

Z-4-5 (3)

N 1.09312500 1.84882500 -0.22107400

N 1.93442300 -0.21902700 0.74293400

N 2.69132500 -1.28370500 0.42809300

C 1.79304800 0.62880000 -0.30828100

C 2.51875700 0.09860800 -1.36184100

H 2.62668700 0.51713700 -2.35151900

C 1.38048800 -0.09431100 2.07054600

H 0.48960500 -0.71983800 2.17860200

H 1.11529600 0.94767300 2.25346700

H 2.13524800 -0.40584100 2.79382200

C 3.03768600 -1.09999100 -0.84461300

H 3.65968000 -1.83197400 -1.34424800

N -0.16100200 1.86011600 -0.10775500

N -2.89288200 -0.31583500 -0.09807200

C -0.96848300 0.73552400 -0.15248800

C -0.81315300 -0.65806300 -0.43185400

H 0.07565500 -1.22708100 -0.66430000

C -2.34419700 0.88725000 0.04964100

H -2.92260100 1.76940400 0.28511300

N -1.98140300 -1.27128500 -0.39843300

C -4.28550700 -0.68106500 0.02678000

H -4.86018800 0.21384900 0.26325600

H -4.63725100 -1.10820300 -0.91467800

H -4.40109500 -1.41592600 0.82639700

Z-4-5 (4)

N -1.01441700 -1.48502200 -0.27372100

N -2.75082200 -0.00615300 0.26971400

N -3.23626200 1.21443300 0.04751000

C -1.51845400 -0.18739600 -0.28714900

C -1.21650700 1.00043500 -0.95574900

H -0.34284600 1.21694300 -1.55090100

C -3.47222000 -0.94217300 1.09976800

H -3.20784000 -0.81360800 2.15337700

H -3.21682100 -1.95531700 0.78669300

H -4.53943900 -0.76481400 0.96580500

C -2.32112800 1.82181000 -0.71479400

H -2.49381700 2.83242400 -1.06195000

N 0.20434400 -1.79301600 -0.31235600

N 2.81621200 0.56020500 0.29320900

C 1.28378500 -0.93059300 -0.18880800

C 2.59534700 -1.42279300 -0.41283400

H 2.87023200 -2.40623200 -0.77241800

69

C 1.49259700 0.37672000 0.27740700

H 0.82091900 1.15292000 0.60700300

N 3.51351500 -0.51536600 -0.13558600

C 3.53167500 1.74686000 0.70456400

H 4.11390700 2.13297100 -0.13503300

H 2.81044500 2.49682000 1.02744000

H 4.20293700 1.50108800 1.53027000

E-5-5 (1)

N 0.45453300 -0.41176800 -0.15268500

N 2.54778100 -0.65950700 -1.20001200

N 3.49967300 0.01232100 -1.83681800

C 1.51554500 0.14829400 -0.82407300

C 1.83660300 1.43634800 -1.25505500

H 1.24361800 2.32894400 -1.12492500

C 2.68116500 -2.08311700 -0.98687300

H 2.72592000 -2.59663900 -1.94993100

H 1.81605800 -2.43066400 -0.42432700

H 3.59451800 -2.28343100 -0.42277000

C 3.07583400 1.28519700 -1.87398700

H 3.68998900 2.03914600 -2.34900800

N -0.45453300 0.41176800 0.15268500

N -2.54778100 0.65950700 1.20001200

N -3.49967300 -0.01232100 1.83681800

C -1.51554500 -0.14829400 0.82407300

C -1.83660300 -1.43634800 1.25505500

H -1.24361800 -2.32894400 1.12492500

C -2.68116500 2.08311700 0.98687300

H -2.72592000 2.59663900 1.94993100

H -1.81605800 2.43066400 0.42432700

H -3.59451800 2.28343100 0.42277000

C -3.07583400 -1.28519700 1.87398700

H -3.68998900 -2.03914600 2.34900800

E-5-5 (2)

N 0.48419900 -0.94465600 -0.00000400

N 2.38436500 0.64726800 -0.00000900

N 3.71524500 0.57156700 -0.00001400

C 1.81457800 -0.59909000 -0.00000800

C 2.86354400 -1.51660600 -0.00001400

H 2.76654500 -2.59250100 -0.00001500

C 1.75876600 1.95303000 -0.00000400

H 1.13670500 2.08069100 0.88779200

H 1.13669500 2.08069300 -0.88779400

70

H 2.56642700 2.68494900 -0.00000700

C 4.01561600 -0.73215900 -0.00001700

H 5.05175700 -1.04323100 -0.00002100

N -0.34074600 0.01484700 0.00000000

N -2.61184700 0.59140400 0.00000700

N -3.84048500 0.08426400 0.00001100

C -1.65810200 -0.38020500 0.00000400

C -2.32853200 -1.60373200 0.00000700

H -1.88381000 -2.58741200 0.00000600

C -2.40140200 2.02273100 0.00000400

H -1.84819500 2.32680800 0.89128600

H -1.84821000 2.32680700 -0.89128900

H -3.38428800 2.49206200 0.00001200

C -3.67670700 -1.24757400 0.00001100

H -4.54592000 -1.89231500 0.00001400

E-5-5 (3)

N -0.32386000 0.54359300 -0.00000100

N -2.47113100 -0.69711800 0.00000000

N -3.76965000 -0.39267200 -0.00000100

C -1.69502800 0.43152700 -0.00000100

C -2.56910000 1.51644600 -0.00000100

H -2.28756300 2.55940900 -0.00000100

C -2.08125900 -2.09170100 0.00000000

H -1.49047200 -2.32546500 0.88739700

H -1.49047200 -2.32546500 -0.88739800

H -3.00346400 -2.67264100 0.00000000

C -3.83989900 0.94298500 -0.00000100

H -4.80659100 1.42875700 -0.00000100

N 0.32386000 -0.54359300 -0.00000100

N 2.47113100 0.69711800 0.00000000

N 3.76965000 0.39267200 -0.00000100

C 1.69502800 -0.43152700 -0.00000100

C 2.56910000 -1.51644600 -0.00000100

H 2.28756300 -2.55940900 -0.00000100

C 2.08125900 2.09170100 0.00000000

H 3.00346400 2.67264100 0.00000000

H 1.49047200 2.32546500 -0.88739800

H 1.49047200 2.32546500 0.88739700

C 3.83989900 -0.94298500 -0.00000100

H 4.80659100 -1.42875700 -0.00000100

Z-5-5 (1)

N -0.64685600 -1.43408700 -0.33944800

71

N -2.49296700 -0.04734500 -0.05696900

N -2.91878900 1.20200100 -0.10946400

C -1.14598600 -0.14723700 -0.28346400

C -0.69271800 1.15908000 -0.51897700

H 0.30743400 1.48615300 -0.75646500

C -3.40335100 -1.11561200 0.29533900

H -3.38991100 -1.28826400 1.37490900

H -3.10238800 -2.02686800 -0.22034200

H -4.40352000 -0.81708100 -0.01704900

C -1.83784700 1.94167200 -0.40472500

H -1.93529200 3.01264800 -0.52294500

N 0.57333000 -1.72362100 -0.43412900

N 1.80634600 0.00942300 0.76936800

N 2.86083800 0.82163500 0.60452400

C 1.57058700 -0.73804400 -0.34183200

C 2.54089600 -0.40539300 -1.27337800

H 2.65021200 -0.81142200 -2.26807300

C 1.11081400 -0.01290500 2.03503400

H 0.42107900 0.83252600 2.10915000

H 0.55237400 -0.94509700 2.12695000

H 1.84823600 0.04309600 2.83679200

C 3.29607000 0.58881100 -0.63284500

H 4.14867300 1.13492600 -1.01586900

Z-5-5 (2)

N 0.62728400 -1.39232900 1.22401700

N 1.33809100 0.82230300 0.34700200

N 2.36304400 1.31778100 -0.35546200

C 1.44273600 -0.53419000 0.48921800

C 2.60815200 -0.91879800 -0.16351800

H 2.98997600 -1.92550800 -0.24956900

C 0.42661400 1.74574500 0.98991400

H 0.07512500 1.32395700 1.93173600

H -0.42654800 1.96843900 0.34414800

H 0.97800000 2.66394900 1.19249300

C 3.11534400 0.26954300 -0.69597500

H 4.00456200 0.41745000 -1.29463000

N -0.62696800 -1.33372600 1.28795500

N -1.33846900 -0.27924700 -0.84769900

N -2.36333100 0.46160100 -1.28389300

C -1.44270700 -0.53152200 0.49272800

C -2.60777600 0.08806200 0.92971200

H -2.98914800 0.09217400 1.94026100

C -0.42719000 -0.84447100 -1.82082900

H 0.42484700 -0.18168100 -1.99165500

72

H -0.07400400 -1.81668200 -1.47672300

H -0.97933900 -0.97336700 -2.75179900

C -3.11517500 0.71575200 -0.21112700

H -4.00445800 1.32447600 -0.30959000

Z-5-5 (3)

N -0.62809700 -1.24412800 -0.02545500

N -2.76191600 -0.32380000 0.12375700

N -3.50617100 0.72908300 -0.18497600

C -1.43804600 -0.13104200 -0.16602700

C -1.35096400 1.14030200 -0.74364000

H -0.47263100 1.62918200 -1.13336200

C -3.35182200 -1.46878900 0.77957900

H -3.32771200 -1.34631300 1.86605400

H -2.78797700 -2.36050600 0.50531400

H -4.38463300 -1.55565300 0.44270700

C -2.66176600 1.61362600 -0.73355000

H -3.03687000 2.56081500 -1.09838600

N 0.62809700 -1.24412800 0.02545500

N 2.76191600 -0.32380000 -0.12375700

N 3.50617100 0.72908400 0.18497600

C 1.43804600 -0.13104200 0.16602700

C 1.35096300 1.14030200 0.74364100

H 0.47263100 1.62918200 1.13336200

C 3.35182200 -1.46878800 -0.77957900

H 4.38463300 -1.55565200 -0.44270700

H 2.78797700 -2.36050500 -0.50531300

H 3.32771300 -1.34631200 -1.86605400

C 2.66176600 1.61362600 0.73355000

H 3.03687000 2.56081600 1.09838600

73

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