4 (4 Fluoro­phen­yl) 3 methyl 6 oxo 1 phenyl 4,5,6,7 tetra­hydro 1H pyrazolo[3,4 b]pyridine 5 carbo­nitrile

organic papers

Acta Cryst.(2006). E62, o47–o48 doi:10.1107/S1600536805039462 Wang and Zhu _C

20H15FN4O

o47

Acta Crystallographica Section E Structure Reports Online

ISSN 1600-5368

4-(4-Fluorophenyl)-3-methyl-6-oxo-1-phenyl-4,5,6,7-tetrahydro-1

H

-pyrazolo[3,4-

b

]pyridine-5-carbonitrile

Jing Wang and Song-Lei Zhu*

Department of Chemistry, Xuzhou Medical College, Xuzhou 221002, People’s Republic of China

Correspondence e-mail: songleizhu@sina.com.cn

Key indicators

Single-crystal X-ray study

T= 298 K

Mean(C–C) = 0.005 A˚

Rfactor = 0.057

wRfactor = 0.165

Data-to-parameter ratio = 13.0

For details of how these key indicators were automatically derived from the article, see http://journals.iucr.org/e.

#2006 International Union of Crystallography Printed in Great Britain – all rights reserved

The title compound, C20H15FN4O, was synthesized by the

reaction of 5-amino-3-methyl-1-phenylpyrazole with ethyl 2-cyano-3-(4-fluorophenyl)-1-acylate in glycol under microwave irradiation. The tetrahydropyridine ring adopts a distorted envelope conformation. The pyrazole ring forms a dihedral angle of 39.2 (3)_{with the attached phenyl ring.}

Comment

The pyrazolo[3,4-b]pyridine system has many interesting

biological and pharmacological properties and is used in the treatment of a wide variety of stress-related illnesses (Seki-kawaet al., 1973; Kuczynskiet al., 1979; El-Deanet al., 1991). As part of our program aimed at employing microwave irra-diation for the preparation of heterocyclic compounds (Tuet al., 2004), we have recently synthesized the title

pyrazolo[3,4-b]pyridine derivative, (I), under microwave irradiation and we report here its crystal structure.

The molecular structure of (I) is shown in Fig. 1. The tetrahydropyridine ring adopts a distorted envelope confor-mation, with atom C1 and C2 deviating from the C3/C4/C5/N1 plane by 0.231 (1) and 0.731 (1) A˚ , respectively, so that C2 is the main flap atom. The pyrazole ring forms a dihedral angle of 39.2 (3) with the attached phenyl ring.

Experimental

A dry flask (25 ml) was charged with 5-amino-3-methyl-1-phenyl-pyrazole (2 mmol), ethyl 2-cyano-3-(4-fluorophenyl)-1-acylate (2 mmol) and glycol (1 ml). The unsealed reaction vessel was put into a modified household microwave oven and connected to refluxing equipment. After microwave irradiation for 5 min (250 W), the reaction mixture was cooled and washed with a small amount of ethanol. The crude product was filtered off and single crystals of (I) were obtained by recrystallization from a 95% ethanol solution (yield

80%). Spectroscopic analysis: IR (KBr,, cm1): 3360, 3074 (NH2),

2228 (CN), 1703 (CO);1_{H NMR (300 MHz, DMSO-d}

6): 2.04 (3H,s,

CH3), 4.96–5.18 (1H,m, CH), 4.68–4.77 (1H,m, CH), 7.16–7.81 (9H, m, ArH), 11.30(1H,s, NH).

Crystal data

C20H15FN4O Mr= 346.36 Orthorhombic,Pbca a= 10.856 (5) A˚

b= 8.245 (4) A˚

c= 38.898 (17) A˚

V= 3482 (3) A˚3 Z= 8

Dx= 1.322 Mg m

3

MoKradiation Cell parameters from 2536

reflections = 2.1–21.1

= 0.09 mm1 T= 298 (2) K Block, colorless 0.450.410.35 mm

Data collection

Bruker SMART CCD area-detector diffractometer

’and!scans

Absorption correction: none 17020 measured reflections 3069 independent reflections

1712 reflections withI> 2(I)

Rint= 0.061

max= 25.0 h=12!12

k=8!9

l=34!46

Refinement

Refinement onF2 R[F2_{> 2(F}2_{)] = 0.057} wR(F2_{) = 0.165} S= 1.03 3069 reflections 236 parameters

H-atom parameters constrained

w= 1/[2_(F

o2) + (0.054P)2

+ 3.1712P]

whereP= (Fo2+ 2Fc2)/3

(/)max< 0.001

max= 0.17 e A˚ 3

min=0.20 e A˚ 3

Table 1

Selected geometric parameters (A˚ ,_).

N1—C1 1.368 (4)

N1—C5 1.389 (4)

C1—C2 1.532 (5)

C2—C3 1.561 (4)

C3—C4 1.503 (4)

C4—C5 1.351 (4)

C1—N1—C5 119.8 (3)

N1—C1—C2 114.5 (3)

C7—C2—C1 109.1 (3)

C7—C2—C3 111.5 (3)

C1—C2—C3 115.3 (2)

C4—C3—C8 115.3 (3)

C4—C3—C2 104.9 (3)

C8—C3—C2 113.8 (3)

C5—C4—C3 121.5 (3)

C4—C5—N1 124.9 (3)

Methyl H atoms were placed in calculated positions, with C—H = 0.96 A˚ and torsion angles refined to fit the electron density, with

Uiso(H) = 1.5Ueq(C). Other H atoms were placed in idealized

posi-tions, with C—H = 0.930.98 A˚ and N—H = 0.86 A˚, and allowed to ride on their parent atoms, withUiso(H) = 1.2Ueq(carrier).

Data collection:SMART(Bruker, 1999); cell refinement:SAINT

(Bruker, 1999); data reduction:SAINT; program(s) used to solve structure:SHELXS97(Sheldrick, 1997); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997); molecular graphics:

SHELXTL (Bruker, 1999); software used to prepare material for publication:SHELXTL.

The authors are deeply indebted to Professor S.-J. Tu and Professor D.-Q. Shi for their invaluable help. We also thank the Key Laboratory of Biotechnology for Medicinal Plants of Jiangsu Province (grant No. 01AXL14) for financial support.

References

Bruker (1999).SMART,SAINTandSHELXTL. Bruker AXS Inc., Madison, Wisconsin, USA.

El-Dean, A. M. K., Atalla, A. A., Mohamed, T. A. & Geies, A. A. (1991).Z. Naturforsch. Teil B,46, 541–546.

Kuczynski, L., Mrozikiewic, A., Banaszkiewicz, W. & Poreba, K. (1979).J. Pharmacol. Pharm.31, 217–225.

Sekikawa, I., Nishie, J., Tono-oka, S., Tanaka, Y. & Kakimoto, S. (1973).J. Heterocycl. Chem.10, 931–932.

Sheldrick, G. M. (1997). SHELXS97 and SHELXL97. University of Go¨ttingen, Germany.

Tu, S.-J., Fang, F., Zhu, S.-L., Li, T.-J., Zhang, X.-J. & Zhuang, Q.-Y. (2004).

Synlett, pp. 537–539. Figure 1

supporting information

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Acta Cryst. (2006). E62, o47–o48

supporting information

Acta Cryst. (2006). E62, o47–o48 [doi:10.1107/S1600536805039462]

4-(4-Fluorophenyl)-3-methyl-6-oxo-1-phenyl-4,5,6,7-tetrahydro-1

H

-pyrazolo-[3,4-

b

]pyridine-5-carbonitrile

Jing Wang and Song-Lei Zhu

S1. Comment

The pyrazolo[3,4-b]pyridine system has many interesting biological and pharmacological properties and is used in the

treatment of a wide variety of stress-related illnesses (Sekikawa et al., 1973; Kuczynski et al., 1979; El-Dean et al.,

1991). As part of our program aimed at employing microwave irradiation for the preparation of heterocyclic compounds

(Tu et al., 2004), we have recently synthesized the title pyrazolo[3,4-b]pyridine derivative, (I), under microwave

irradiation and we report here its crystal structure.

The molecular structure of (I) is shown in Fig. 1. The tetrahydropyridine ring adopts a distorted envelope conformation,

with atom C1 and C2 deviating from the C3/C4/C5/N1 plane by 0.231 (1) and 0.731 (1) Å, respectively. The dihedral

angle of 0.62 (3)° between the C3/C4/C5/N1 plane and the fused pyrazole plane indicates they are coplanar. The pyrazole

ring forms a dihedral angle of 39.2 (3)° with the attached phenyl ring.

S2. Experimental

A dry flask (25 ml) was charged with 5-amino-3-methyl-1-phenylpyrazole (2 mmol), ethyl

2-cyano-3-(4-fluorophenyl)-1-acylate (2 mmol) and 1 ml glycol as energy transfer. The unsealed reaction vessel was put into a modified household

microwave oven and connected with refluxing equipment. After microwave irradiation for 5 min (250 W), the reaction

mixture was cooled and washed with small amount ethanol. The crude product was filtered and single crystals of (I) were

obtained by recrystallization from a 95% ethanol solution (yield 80%). Spectroscopic analysis: IR (KBr, ν, cm−1_{): 3360,}

3074 (NH2), 2228 (CN), 1703 (CO); 1H NMR (300 MHz, DMSO-d6): 2.04 (3H, s, CH3), 4.96–5.18 (1H, m, CH), 4.68–

4.77 (1H, m, CH), 7.16–7.81 (9H, m, ArH), 11.30(1H, s, NH).

S3. Refinement

Methyl H atoms were placed in calculated positions, with C—H = 0.96 Å and torsion angles refined to fit the electron

density, with Uiso(H) = 1.5Ueq(C). Other H atoms were placed in idealized positions, with C—H = 0.93 − 0.98 Å and N—

Figure 1

The molecular structure of (I), showing 40% probability displacement ellipsoids (arbitrary spheres for H atoms).

4-(4-Fluorophenyl)-3-methyl-6-oxo-1-phenyl-4,5,6,7-tetrahydro-1H- pyrazolo[3,4-b]pyridine-5-carbonitrile

Crystal data C20H15FN4O

Mr = 346.36

Orthorhombic, Pbca Hall symbol: -P 2ac 2ab a = 10.856 (5) Å b = 8.245 (4) Å c = 38.898 (17) Å V = 3482 (3) Å3

Z = 8

F(000) = 1440

Dx = 1.322 Mg m−3

Melting point = 497–498 K Mo Kα radiation, λ = 0.71073 Å Cell parameters from 2536 reflections θ = 2.1–21.1°

µ = 0.09 mm−1

T = 298 K Block, colorless 0.45 × 0.41 × 0.35 mm

Data collection

Bruker SMART CCD area-detector diffractometer

Radiation source: fine-focus sealed tube Graphite monochromator

φ and ω scans

17020 measured reflections 3069 independent reflections

1712 reflections with I > 2σ(I) Rint = 0.061

θmax = 25.0°, θmin = 2.1°

h = −12→12 k = −8→9 l = −34→46

Refinement Refinement on F2

Least-squares matrix: full R[F2 _{> 2σ(F}2_{)] = 0.057}

wR(F2_{) = 0.165}

S = 1.03 3069 reflections 236 parameters 0 restraints

Secondary atom site location: difference Fourier map

Hydrogen site location: inferred from neighbouring sites

H-atom parameters constrained w = 1/[σ2_(F

o2) + (0.054P)2 + 3.1712P]

where P = (Fo2 + 2Fc2)/3

supporting information

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Acta Cryst. (2006). E62, o47–o48

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F2 _{against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F}2_,

conventional R-factors R are based on F, with F set to zero for negative F2_{. The threshold expression of F}2 _{> σ(F}2_{) is used}

only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2

are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2₎

x y z Uiso*/Ueq

F1 0.5985 (3) 0.3427 (4) 0.49399 (7) 0.1356 (12)

N1 0.4743 (2) 0.1085 (3) 0.66799 (7) 0.0479 (7)

H1 0.4430 0.1726 0.6831 0.058*

N2 0.2834 (2) −0.0461 (3) 0.66026 (7) 0.0468 (7)

N3 0.2384 (2) −0.1592 (3) 0.63736 (7) 0.0511 (7)

N4 0.8660 (3) 0.0407 (4) 0.61601 (9) 0.0696 (9)

O1 0.6632 (2) 0.2236 (3) 0.67158 (6) 0.0589 (7)

C1 0.5971 (3) 0.1169 (4) 0.66039 (8) 0.0462 (8)

C2 0.6450 (2) −0.0233 (4) 0.63825 (9) 0.0463 (8)

H2 0.6520 −0.1179 0.6534 0.056*

C3 0.5599 (3) −0.0737 (4) 0.60773 (8) 0.0450 (8)

H3 0.5860 −0.1817 0.6001 0.054*

C4 0.4338 (3) −0.0907 (4) 0.62334 (8) 0.0447 (8)

C5 0.4001 (3) −0.0040 (4) 0.65128 (8) 0.0443 (8)

C6 0.3311 (3) −0.1871 (4) 0.61542 (9) 0.0477 (8)

C7 0.7699 (3) 0.0152 (4) 0.62641 (9) 0.0525 (9)

C8 0.5677 (3) 0.0389 (4) 0.57698 (9) 0.0472 (8)

C9 0.6277 (4) −0.0099 (5) 0.54775 (10) 0.0795 (13)

H9 0.6622 −0.1131 0.5468 0.095*

C10 0.6378 (5) 0.0929 (7) 0.51946 (11) 0.1000 (16)

H10 0.6781 0.0592 0.4996 0.120*

C11 0.5878 (4) 0.2421 (6) 0.52155 (10) 0.0813 (13)

C12 0.5286 (4) 0.2951 (5) 0.54961 (10) 0.0719 (11)

H12 0.4950 0.3989 0.5502 0.086*

C13 0.5183 (3) 0.1936 (4) 0.57759 (9) 0.0581 (9)

H13 0.4774 0.2296 0.5972 0.070*

C14 0.2059 (3) 0.0187 (4) 0.68625 (9) 0.0489 (8)

C15 0.0829 (3) 0.0493 (5) 0.67888 (10) 0.0618 (10)

H15 0.0513 0.0240 0.6573 0.074*

C16 0.0082 (4) 0.1170 (6) 0.70340 (12) 0.0799 (13)

H16 −0.0749 0.1343 0.6988 0.096*

C17 0.0563 (4) 0.1593 (6) 0.73481 (13) 0.0911 (15)

H17 0.0064 0.2096 0.7511 0.109*

C18 0.1774 (4) 0.1280 (6) 0.74243 (11) 0.0914 (15)

C19 0.2525 (4) 0.0561 (5) 0.71824 (9) 0.0683 (11)

H19 0.3342 0.0331 0.7235 0.082*

C20 0.3188 (3) −0.3058 (5) 0.58706 (9) 0.0667 (11)

H20A 0.2540 −0.3810 0.5923 0.100*

H20B 0.3949 −0.3637 0.5843 0.100*

H20C 0.2996 −0.2497 0.5661 0.100*

Atomic displacement parameters (Å2₎

U11 _U22 _U33 _U12 _U13 _U23

F1 0.201 (3) 0.136 (3) 0.0688 (17) 0.016 (2) 0.0285 (19) 0.0418 (18)

N1 0.0346 (14) 0.0499 (17) 0.0592 (18) −0.0046 (13) 0.0005 (12) −0.0043 (14)

N2 0.0359 (14) 0.0485 (17) 0.0560 (17) −0.0087 (13) −0.0018 (12) 0.0018 (13)

N3 0.0400 (15) 0.0506 (18) 0.0628 (18) −0.0125 (13) −0.0065 (14) 0.0014 (14)

N4 0.0414 (17) 0.066 (2) 0.101 (3) −0.0054 (16) 0.0015 (17) 0.0100 (18)

O1 0.0483 (13) 0.0606 (16) 0.0679 (16) −0.0215 (12) −0.0073 (11) −0.0004 (13)

C1 0.0380 (18) 0.049 (2) 0.052 (2) −0.0054 (16) −0.0073 (15) 0.0135 (16)

C2 0.0297 (16) 0.0400 (19) 0.069 (2) −0.0011 (14) −0.0055 (15) 0.0145 (16)

C3 0.0347 (16) 0.0344 (18) 0.066 (2) −0.0003 (14) 0.0011 (15) −0.0011 (16)

C4 0.0349 (16) 0.0435 (19) 0.056 (2) −0.0051 (15) −0.0046 (15) 0.0039 (16)

C5 0.0306 (16) 0.045 (2) 0.057 (2) −0.0051 (14) −0.0063 (15) 0.0077 (17)

C6 0.0386 (17) 0.045 (2) 0.059 (2) −0.0042 (15) −0.0061 (16) 0.0054 (17)

C7 0.0363 (19) 0.048 (2) 0.074 (2) −0.0001 (16) −0.0085 (17) 0.0060 (18)

C8 0.0363 (17) 0.047 (2) 0.058 (2) −0.0011 (16) 0.0007 (15) −0.0040 (17)

C9 0.092 (3) 0.076 (3) 0.071 (3) 0.030 (3) 0.020 (2) −0.003 (2)

C10 0.129 (4) 0.114 (4) 0.056 (3) 0.027 (4) 0.030 (3) 0.004 (3)

C11 0.105 (3) 0.086 (3) 0.053 (3) 0.003 (3) 0.005 (2) 0.021 (2)

C12 0.090 (3) 0.064 (3) 0.062 (3) 0.009 (2) 0.004 (2) 0.013 (2)

C13 0.065 (2) 0.053 (2) 0.056 (2) 0.0035 (19) 0.0079 (18) 0.0020 (18)

C14 0.0394 (17) 0.055 (2) 0.053 (2) −0.0078 (16) 0.0052 (15) 0.0059 (17)

C15 0.0405 (19) 0.084 (3) 0.061 (2) −0.0038 (19) 0.0048 (17) 0.008 (2)

C16 0.047 (2) 0.106 (4) 0.087 (3) −0.001 (2) 0.020 (2) 0.002 (3)

C17 0.074 (3) 0.114 (4) 0.085 (3) −0.019 (3) 0.038 (3) −0.013 (3)

C18 0.080 (3) 0.133 (4) 0.061 (3) −0.028 (3) 0.012 (2) −0.011 (3)

C19 0.052 (2) 0.090 (3) 0.063 (2) −0.017 (2) 0.002 (2) 0.002 (2)

C20 0.059 (2) 0.070 (3) 0.071 (3) −0.020 (2) 0.0012 (19) −0.006 (2)

Geometric parameters (Å, º)

F1—C11 1.360 (5) C9—C10 1.393 (6)

N1—C1 1.368 (4) C9—H9 0.9300

N1—C5 1.389 (4) C10—C11 1.347 (6)

N1—H1 0.8600 C10—H10 0.9300

N2—C5 1.359 (4) C11—C12 1.340 (6)

N2—N3 1.379 (4) C12—C13 1.377 (5)

N2—C14 1.420 (4) C12—H12 0.9300

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Acta Cryst. (2006). E62, o47–o48

O1—C1 1.216 (4) C14—C15 1.388 (5)

C1—C2 1.532 (5) C15—C16 1.371 (5)

C2—C7 1.466 (4) C15—H15 0.9300

C2—C3 1.561 (4) C16—C17 1.374 (6)

C2—H2 0.9800 C16—H16 0.9300

C3—C4 1.503 (4) C17—C18 1.372 (6)

C3—C8 1.516 (5) C17—H17 0.9300

C3—H3 0.9800 C18—C19 1.379 (5)

C4—C5 1.351 (4) C18—H18 0.9300

C4—C6 1.403 (4) C19—H19 0.9300

C6—C20 1.481 (5) C20—H20A 0.9600

C8—C9 1.370 (5) C20—H20B 0.9600

C8—C13 1.385 (5) C20—H20C 0.9600

C1—N1—C5 119.8 (3) C10—C9—H9 119.5

C1—N1—H1 120.1 C11—C10—C9 118.4 (4)

C5—N1—H1 120.1 C11—C10—H10 120.8

C5—N2—N3 109.7 (3) C9—C10—H10 120.8

C5—N2—C14 129.7 (3) C12—C11—C10 122.7 (4)

N3—N2—C14 120.3 (2) C12—C11—F1 118.9 (5)

C6—N3—N2 105.2 (2) C10—C11—F1 118.4 (4)

O1—C1—N1 122.3 (3) C11—C12—C13 119.0 (4)

O1—C1—C2 123.2 (3) C11—C12—H12 120.5

N1—C1—C2 114.5 (3) C13—C12—H12 120.5

C7—C2—C1 109.1 (3) C12—C13—C8 121.0 (3)

C7—C2—C3 111.5 (3) C12—C13—H13 119.5

C1—C2—C3 115.3 (2) C8—C13—H13 119.5

C7—C2—H2 106.8 C19—C14—C15 119.9 (3)

C1—C2—H2 106.8 C19—C14—N2 120.6 (3)

C3—C2—H2 106.8 C15—C14—N2 119.4 (3)

C4—C3—C8 115.3 (3) C16—C15—C14 120.0 (4)

C4—C3—C2 104.9 (3) C16—C15—H15 120.0

C8—C3—C2 113.8 (3) C14—C15—H15 120.0

C4—C3—H3 107.5 C15—C16—C17 119.8 (4)

C8—C3—H3 107.5 C15—C16—H16 120.1

C2—C3—H3 107.5 C17—C16—H16 120.1

C5—C4—C6 105.1 (3) C18—C17—C16 120.6 (4)

C5—C4—C3 121.5 (3) C18—C17—H17 119.7

C6—C4—C3 133.4 (3) C16—C17—H17 119.7

C4—C5—N2 108.9 (3) C17—C18—C19 120.0 (4)

C4—C5—N1 124.9 (3) C17—C18—H18 120.0

N2—C5—N1 126.2 (3) C19—C18—H18 120.0

N3—C6—C4 111.1 (3) C14—C19—C18 119.7 (4)

N3—C6—C20 121.3 (3) C14—C19—H19 120.2

C4—C6—C20 127.5 (3) C18—C19—H19 120.2

N4—C7—C2 177.0 (4) C6—C20—H20A 109.5

C9—C8—C13 117.9 (3) C6—C20—H20B 109.5

C13—C8—C3 121.9 (3) C6—C20—H20C 109.5

C8—C9—C10 121.0 (4) H20A—C20—H20C 109.5

C8—C9—H9 119.5 H20B—C20—H20C 109.5

C5—N2—N3—C6 1.9 (3) C3—C4—C6—N3 179.6 (3)

C14—N2—N3—C6 176.4 (3) C5—C4—C6—C20 −179.8 (3)

C5—N1—C1—O1 172.2 (3) C3—C4—C6—C20 −0.7 (6)

C5—N1—C1—C2 −10.7 (4) C4—C3—C8—C9 −132.2 (4)

O1—C1—C2—C7 −13.8 (4) C2—C3—C8—C9 106.5 (4)

N1—C1—C2—C7 169.2 (3) C4—C3—C8—C13 49.4 (4)

O1—C1—C2—C3 −140.1 (3) C2—C3—C8—C13 −71.8 (4)

N1—C1—C2—C3 42.8 (4) C13—C8—C9—C10 −0.4 (6)

C7—C2—C3—C4 −173.9 (3) C3—C8—C9—C10 −178.9 (4)

C1—C2—C3—C4 −48.8 (3) C8—C9—C10—C11 0.4 (8)

C7—C2—C3—C8 −47.1 (4) C9—C10—C11—C12 −0.3 (8)

C1—C2—C3—C8 78.0 (3) C9—C10—C11—F1 179.6 (4)

C8—C3—C4—C5 −97.6 (4) C10—C11—C12—C13 0.1 (7)

C2—C3—C4—C5 28.3 (4) F1—C11—C12—C13 −179.7 (4)

C8—C3—C4—C6 83.4 (4) C11—C12—C13—C8 −0.1 (6)

C2—C3—C4—C6 −150.6 (3) C9—C8—C13—C12 0.3 (5)

C6—C4—C5—N2 0.6 (4) C3—C8—C13—C12 178.7 (3)

C3—C4—C5—N2 −178.5 (3) C5—N2—C14—C19 −41.8 (5)

C6—C4—C5—N1 −179.9 (3) N3—N2—C14—C19 144.9 (3)

C3—C4—C5—N1 0.9 (5) C5—N2—C14—C15 136.0 (4)

N3—N2—C5—C4 −1.6 (4) N3—N2—C14—C15 −37.2 (5)

C14—N2—C5—C4 −175.4 (3) C19—C14—C15—C16 0.1 (6)

N3—N2—C5—N1 179.0 (3) N2—C14—C15—C16 −177.8 (4)

C14—N2—C5—N1 5.1 (5) C14—C15—C16—C17 2.2 (7)

C1—N1—C5—C4 −11.9 (5) C15—C16—C17—C18 −2.8 (7)

C1—N1—C5—N2 167.5 (3) C16—C17—C18—C19 1.2 (8)

N2—N3—C6—C4 −1.5 (4) C15—C14—C19—C18 −1.8 (6)

N2—N3—C6—C20 178.8 (3) N2—C14—C19—C18 176.1 (4)