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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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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.
(E)-1-methyl-5-((1-methyl-1H-pyrazol-4-yl)diazenyl)-1H-pyrazole (4-5)
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.
(E)-1,2-bis(1-methyl-1H-pyrazol-3-yl)diazene (3-3)
(E)-1-methyl-5-((1-methyl-1H-pyrazol-3-yl)diazenyl)-1H-pyrazole (3-5)
(E)-1,2-bis(1-methyl-1H-pyrazol-5-yl)diazene (5-5)
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
Figure S3. 1H NMR spectra of E-3-5 and its PSS in CD3CN.
9
Figure S4. 1H NMR spectra of E-4-4 and its PSS in CD3CN.
10
Figure S5. 1H NMR spectra of E-4-5 and its PSS in CD3CN.
11
Figure S6. 1H NMR spectra of E-5-5 and its PSS in CD3CN.
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.
14
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
Figure S11. UV-Vis first-order kinetics analysis and Arrhenius plot for thermal Z→E isomerization of 3-4.
Table S3. Thermal isomerization kinetics results of 3-4 in DMSO.
Experimental Calculated
65 ºC 70 ºC 75 ºC 80 ºC 25 ºC
k (min-1) 1.28×10-4 2.22×10-4 3.83×10-4 6.46×10-4 k (min-1) 7.73×10-7 Ea (kJ/mol) 107.1
t1/2 (min) 5398 3127 1810 1073 t1/2 (d) 623 ln A 25.0
19
Figure S12. UV-Vis first-order kinetics analysis and Arrhenius plot for thermal Z→E isomerization of 3-5.
Table S4. Thermal isomerization kinetics results of 3-5 in DMSO.
Experimental Calculated
35 ºC 40 ºC 45 ºC 50 ºC 25 ºC
k (min-1) 2.81×10-4 5.09×10-4 8.86×10-4 1.54×10-3 k (min-1) 8.25×10-5 Ea (kJ/mol) 93.8
t1/2 (min) 2471 1362 783 450 t1/2 (d) 6 ln A 24.3
20
Figure S13. UV-Vis first-order kinetics analysis and Arrhenius plot for thermal Z→E isomerization of 4-4.
Table S5. Thermal isomerization kinetics results of 4-4 in DMSO.
Experimental Calculated
65 ºC 70 ºC 75 ºC 80 ºC 25 ºC
k (min-1) 1.25×10-4 2.21×10-4 3.73×10-4 6.48×10-4 k (min-1) 7.07×10-7 Ea (kJ/mol) 108.4
t1/2 (min) 5545 3136 1857 1069 t1/2 (d) 681 ln A 25.5
21
Figure S14. UV-Vis first-order kinetics analysis and Arrhenius plot for thermal Z→E isomerization of 4-5.
Table S6. Thermal isomerization kinetics results of 4-5 in DMSO.
Experimental Calculated
45 ºC 50 ºC 55 ºC 60 ºC 25 ºC
k (min-1) 2.30×10-4 4.06×10-4 7.09×10-4 1.22×10-3 k (min-1) 1.91×10-5 Ea (kJ/mol) 98.1
t1/2 (min) 3016 1705 978 568 t1/2 (d) 25 ln A 24.6
22
Figure S15. UV-Vis first-order kinetics analysis and Arrhenius plot for thermal Z→E isomerization of 5-5.
Table S7. Thermal isomerization kinetics results of 5-5 in DMSO.
Experimental Calculated
25 ºC 30 ºC 35 ºC 40 ºC 25 ºC
k (min-1) 1.62×10-3 2.93×10-3 5.23×10-3 8.97×10-3 k (min-1) 1.62×10-3 Ea (kJ/mol) 88.7
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
Figure S17. Crystal structure of E-3-4 (ellipsoid model).
Table S9. Crystal data and structure refinement of E-3-4.
Empirical formula C8H10N6
Formula weight 190.22
Temperature 173(2) K
Wavelength 1.54178 Å
Crystal system Orthorhombic
Space group P 21 21 21
Unit cell dimensions
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
Absorption coefficient 0.758 mm-1
F(000) 400
Crystal size 0.15 × 0.14 × 0.12 mm
Theta range for data collection 5.697 to 68.350°
Index ranges -9 ≤ h ≤ 9, -12 ≤ k ≤ 12, -12 ≤ l ≤ 13
Reflections collected 13499
Independent reflections 1702 (Rint = 0.0378)
Completeness to theta = 67.679 99.4%
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 1702 / 0 / 129
Goodness-of-fit on F2 1.090
Final R indices [I > 2sigma(I)] R1 = 0.0293, wR2 = 0.0776
R indices (all data) R1 = 0.0309, wR2 = 0.0791
Largest diff. peak and hole 0.172 and -0.153 e.Å-3
25
Figure S18. Crystal structure of E-3-5 (ellipsoid model).
Table S10. Crystal data and structure refinement of E-3-5.
Empirical formula C8H10N6
Formula weight 190.22
Temperature 297(2) K
Wavelength 1.54178 Å
Crystal system Monoclinic
Space group P 21/n
Unit cell dimensions
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
Density (calculated) 1.321 Mg/m3
Absorption coefficient 0.738 mm-1
F(000) 400
Crystal size 0.24 × 0.20 × 0.20 mm
Theta range for data collection 4.436 to 66.784°
Index ranges -12 ≤ h ≤ 12, -7 ≤ k ≤ 7, -17 ≤ l ≤ 18
Reflections collected 6057
Independent reflections 1670 (Rint = 0.0449)
Completeness to theta = 67.679 98.1%
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 1670 / 0 / 129
Goodness-of-fit on F2 1.031
Final R indices [I > 2sigma(I)] R1 = 0.0569, wR2 = 0.1562
R indices (all data) R1 = 0.0713, wR2 = 0.1712
Largest diff. peak and hole 0.291 and -0.201 e.Å-3
26
Figure S19. Crystal structure of E-4-4 (ellipsoid model).
Table S11. Crystal data and structure refinement of E-4-4.
Empirical formula C8H10N6
Formula weight 190.22
Temperature 299(2) K
Wavelength 1.54178 Å
Crystal system Monoclinic
Space group P 21/c
Unit cell dimensions
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
Density (calculated) 1.298 Mg/m3
Absorption coefficient 0.725 mm-1
F(000) 200
Crystal size 0.18 × 0.16 × 0.12 mm
Theta range for data collection 7.917 to 68.143°
Index ranges -8 ≤ h ≤ 8, -12 ≤ k ≤ 12, -8 ≤ l ≤ 8
Reflections collected 6538
Independent reflections 887 (Rint = 0.0308)
Completeness to theta = 67.679 99.2%
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 887 / 0 / 66
Goodness-of-fit on F2 1.073
Final R indices [I > 2sigma(I)] R1 = 0.0544, wR2 = 0.1458
R indices (all data) R1 = 0.0589, wR2 = 0.1513
Largest diff. peak and hole 0.203 and -0.187 e.Å-3
27
Figure S20. Crystal structure of E-4-5 (ellipsoid model).
Table S12. Crystal data and structure refinement of E-4-5.
Empirical formula C8H10N6
Formula weight 190.22
Temperature 296(2) K
Wavelength 1.54178 Å
Crystal system Monoclinic
Space group P 21
Unit cell dimensions
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
Density (calculated) 1.313 Mg/m3
Absorption coefficient 0.733 mm-1
F(000) 200
Crystal size 0.2 × 0.2 × 0.2 mm
Theta range for data collection 4.586 to 68.310°
Index ranges -4 ≤ h ≤ 4, -14 ≤ k ≤ 14, -10 ≤ l ≤ 11
Reflections collected / unique 2972
Independent reflections 1646 (Rint = 0.0408)
Completeness to theta = 67.679 98.3%
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 1646 / 1 / 129
Goodness-of-fit on F2 1.105
Final R indices [I > 2sigma(I)] R1 = 0.0415, wR2 = 0.0997
R indices (all data) R1 = 0.0568, wR2 = 0.1125
Largest diff. peak and hole 0.120 and -0.164 e.Å-3
28
Figure S21. Crystal structure of E-5-5 (ellipsoid model).
Table S13. Crystal data and structure refinement of E-5-5.
Empirical formula C8H10N6
Formula weight 190.22
Temperature 297(2) K
Wavelength 1.54178 Å
Crystal system Monoclinic
Space group P 21/c
Unit cell dimensions
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
Density (calculated) 1.313 Mg/m3
Absorption coefficient 0.733 mm-1
F(000) 200
Crystal size 0.25 × 0.24 × 0.2 mm
Theta range for data collection 5.906 to 68.270°
Index ranges -9 ≤ h ≤ 7, -7 ≤ k ≤ 8, -10 ≤ l ≤ 10
Reflections collected 2526
Independent reflections 858 (Rint = 0.0192)
Completeness to theta = 67.679 96.9%
Refinement method Full-matrix least-squares on F2
Data / restraints / parameters 858 / 0 / 65
Goodness-of-fit on F2 1.079
Final R indices [I > 2sigma(I)] R1 = 0.0447, wR2 = 0.1237
R indices (all data) R1 = 0.0484, wR2 = 0.1295
Largest diff. peak and hole 0.244 and -0.150 e.Å-3
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.
37
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
Figure S26. The frontier molecular orbitals (FMOs) and natural transition orbitals (NTOs) of 3-4 (isosurface
value of 0.05).
41
Figure S27. The frontier molecular orbitals (FMOs) and natural transition orbitals (NTOs) of 3-5 (isosurface
value of 0.05).
42
43
Figure S28. The frontier molecular orbitals (FMOs) and natural transition orbitals (NTOs) of 4-4 (isosurface
value of 0.05).
44
45
Figure S29. The frontier molecular orbitals (FMOs) and natural transition orbitals (NTOs) of 4-5 (isosurface
value of 0.05).
46
Figure S30. The frontier molecular orbitals (FMOs) and natural transition orbitals (NTOs) of 5-5 (isosurface
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
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50
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Z-3-3 (2)
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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
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N -2.69147200 0.77912800 0.31004900
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C -2.52488800 -1.20016900 -0.71261400
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H -4.76574200 -0.68733300 1.44136000
E-3-4 (1)
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N 0.40910900 0.49385900 -0.00004300
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52
N 3.90029600 0.08043400 0.00003900
C 5.28946600 0.47452400 0.00006400
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H 5.78486500 0.08319100 -0.89145200
H 5.34302300 1.56294900 -0.00003700
E-3-4 (2)
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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
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N 0.37706800 -0.23162400 -0.00000700
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N -3.71428100 -0.45245600 0.00000400
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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
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C 2.37731500 1.24028000 0.00000100
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C -2.77263700 1.53624200 0.00000000
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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
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N 3.68151500 1.01790000 0.00000100
N 3.81832500 -0.32636500 0.00000100
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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
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C -2.55539200 1.63714000 -0.00003000
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N -0.33274800 0.57631500 -0.00000500
C -4.77441500 -1.20138500 -0.00002100
H -5.72796000 -0.67354100 -0.00006600
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H 4.74325000 2.00129600 0.00001200
Z-3-4 (1)
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N -0.54995400 -1.79328000 -0.00049500
C 1.69016600 -0.94684800 -0.00023500
54
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H -0.32665400 1.37600800 0.00009200
C 3.05339400 -1.33258100 0.00000900
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C 3.74935200 -0.14746800 0.00011900
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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
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N -2.41666800 1.34692500 0.00020000
N -3.30906400 0.32952300 0.00003200
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H -4.97811100 1.20212000 -0.89126400
H -5.27657000 -0.31398900 0.00005400
Z-3-4 (2)
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N -0.59010900 1.81578000 0.03011600
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H -0.40130200 -1.13659700 -0.96142100
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H 4.59358700 -0.86750700 -1.59215900
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N -3.32939200 -0.37101700 -0.07348100
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55
H -4.78137700 -1.56399000 0.83579000
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Z-3-4 (3)
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N -0.50865400 -2.04344600 0.00003400
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N -2.69726700 0.78893000 0.00009700
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H -3.82939400 2.29523400 -0.89137200
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Z-3-4 (4)
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N 0.62977600 -2.02196600 -0.13828000
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56
H -5.06994500 0.13927800 -0.56583500
N -2.50069300 -0.63335400 -0.57679200
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N 2.69412100 0.89252500 -0.17046500
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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)
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N -3.64005900 -0.13585900 -0.00503300
N -0.26075600 -0.60018200 0.00003700
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N 4.15792300 -0.10241000 -0.00085200
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H -4.12719100 1.93551800 -0.00010900
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C -1.53031600 -0.04588100 0.00099700
C -4.95459100 -0.73714200 0.00179600
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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
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57
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C -4.22761600 -0.67577000 -0.00003000
H -5.25579700 -1.01252200 -0.00003900
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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
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C -2.03027200 -0.48990800 -0.00002500
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C 4.74558900 0.94241000 0.00002600
H 4.78513600 1.57211200 0.89176600
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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
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N -2.16999300 -0.74081300 -0.00057600
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C -1.46009000 0.39835100 0.00059200
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58
E-3-5 (4)
N -0.56903300 0.06670800 0.00001300
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N -2.81575900 0.76913200 0.00015100
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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
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C -1.91022000 -0.24936900 0.00007800
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Z-3-5 (1)
N -0.97600700 -1.88994700 -0.33629200
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N 0.26121500 -2.03806900 -0.18131100
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N -2.51132100 1.23803900 0.48247700
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C -2.88419800 1.10265000 -0.78863300
H -3.52187900 1.84893000 -1.24553300
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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)
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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
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H -4.53780500 -0.46059900 1.15296900
Z-3-5 (3)
N -0.96398300 -1.33645100 0.00000500
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N -2.86825800 -0.06832300 0.00000600
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C -2.33681600 1.98323100 -0.00003000
60
H -2.50290300 3.05271900 -0.00004500
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C -3.73584600 -1.22711400 0.00003400
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C -1.12708900 1.29425200 -0.00002900
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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)
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N -0.32184400 -1.50444700 -0.38100000
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N 2.89384200 -0.18892500 0.12791300
N 3.50966600 0.98582600 0.04540800
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H -0.44034900 1.10226500 1.26922500
C 2.59689900 1.82851000 -0.45393000
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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
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C 1.36800100 1.20022400 -0.65922200
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C -4.70643900 0.11615600 -0.19766700
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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
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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
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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
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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
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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
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N 3.77908900 -0.20180200 0.00000300
C 5.00711800 -0.96314800 -0.00000100
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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
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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
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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
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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
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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
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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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