CIF access

Acta Cryst. (1999). C55, IUC9900168

[ doi:10.1107/S0108270199098273 ]

Three 3-aryl-5-cyanopyrazolo[3,4-b]pyridines
J. Quiroga, S. Cruz, B. Insuasty, M. Nogueras, A. Snchez, J. Cobo and J. N. Low
Abstract
4-(4-Chlorophenyl)-5-cyano-3-(4-methylphenyl)-6-diphenyl-4,7-dihydro-2H- pyrazolo[3,4-b]pyridinedimethyl formamide (2/1), 2C26H19ClN4C3H7NO, (I), 5-cyano-4-(4-methoxyphenyl)-3,6-diphenyl-4,7-dihydro-2H-pyrazolo[3,4-b]- pyridine, C26H20N4O, (II), and 3,4-bis(4-chlorophenyl)-5-cyano-6-phenyl-1H-pyrazolo[3,4-b]pyridine, C25H14Cl2N4, (III),
were prepared from the corresponding 3-amino-5-arylpyrazoles and -cyanochalcones. NMR solution studies (1H, 13 C,
HSQC, HMBC, NOESY) of pyrazolo[3,4-b]pyridines, reveal the 2H-tautomers as being preferred in solution (DMSO-d6).
X-ray diffraction studies showed that (I) and (II) also have the 2H-tautomeric structures in the crystal structures. (III) is the
aromatic crystalline product formed by oxidation of a 2H precusor during re-crystallization. (I) exists as hydrogen-bonded
trimers (two pyrazolo[3,4-b]pyridine systems and a dimethyl formamide), (II) forms two-dimensional sheets and (III) is a
centrosymmetric dimer. A paper discussing the chemistry of the above compounds is being prepared

Experimental
4-(4-Chlorophenyl)-5-cyano-3-(4-methylphenyl)-6-diphenyl-4,7-dihydro-2H-

pyrazolo[3,4-

b]pyridinedimethylformamide (2/1), (I): a solution of 1.40 mmol of 3-amine-5-(4-methylphenyl)-1H-pyrazole and 1.40

mmol of 2-benzoyl-3-(4-chlorophenyl)-2-propenenitrile was heated in 50 ml of absolute ethanol for 12 h. After cooling,
the reaction mixture was allowed to stand overnight. The resulting precipitate was filtered off, washed with cold ethanol
and recrystallized from dimethyl formamide.
5-Cyano-4-(4-methoxyphenyl)-3,6-diphenyl-4,7-dihydro-2H-pyrazolo [3,4-b]pyridine, (II): a solution of 1.40 mmol of
3-amine-5-phenyl-1H-pyrazole and 1.40 mmol of 2-benzoyl-3-(4-methoxyphenyl)-2-propenenitrile was heated in 50 ml of
absolute ethanol for 12 h. After cooling, the reaction mixture was allowed to stand overnight. The resulting precipitate was
filtered off, washed with cold ethanol and recrystallized from ethanol.
3,4-Bis(4-chlorophenyl)-5-cyano-6-phenyl-1H-pyrazolo-[3,4-b]pyridine, (III): a solution of 1.40 mmol of 3-amine-5-(4chlorophenyl)-1H-pyrazole and 1.40 mmol of 2-benzoyl-3-(4-chlorophenyl)-2-propenenitrile was heated in 50 ml of absolute ethanol for 12 h. After cooling, the reaction mixture was allowed to stand overnight. The resulting precipitate was
filtered off, washed with cold ethanol and recrystallized from ethanol.
Refinement
Compound (I) crystallized in the triclinic system; space group P1 assumed and confirmed by structure analysis. There are
two independent molecules of the 2H-pyrazolo[3,4-b]pyridine derivative and one of the crystallization solvent (dimethyl
formamide) in the asymmetric unit. Molecule (II) crystallized in the monoclinic system; space group C2/c or Cc from
systematic absences; C2/c chosen and confirmed by the analysis. Molecule (III) crystallized in the monoclinic system; space
group P21/n from systematic absences. In all structures, H atoms were treated as riding atoms with CH 0.951.00 ,

CIF access
NH 0.88 . Examination of the structures with PLATON (Spek, 1999) showed that there were no solvent-accessible voids
in the crystal lattices.
Computing details
For all compounds, data collection: KappaCCD Server Software (Nonius, 1997); cell refinement: DENZO (Otwinowski
& Minor, 1997); data reduction: DENZO (Otwinowski & Minor, 1997); program(s) used to solve structure:
SHELXS97 (Sheldrick, 1997a); program(s) used to refine structure: SHELXL97 (Sheldrick, 1997b); molecular graphics:
ORTEPII (Johnson, 1976) and PLATON (Spek, 1999); software used to prepare material for publication: SHELXL97 and
WORDPERFECT macro PRPKAPPA (Ferguson, 1999)

4-(4-chlorophenyl)-5-cyano-3-(4-methylphenyl)-6-diphenyl-4,7-dihydro-2H-pyrazolo [3,4b]pyridine:dimethylformamide (2/1)

Crystal data
2C26H19ClN4C3H7NO

= 99.610 (2)

Mr = 918.90

V = 2322.64 (15) 3
Z=2
Mo K

Triclinic, P1
a = 12.4124 (5)
b = 13.8275 (4)
c = 14.3744 (6)
= 91.747 (2)
= 106.6376 (17)

= 0.19 mm1
T = 150.0 (1) K
0.2 0.2 0.15 mm

Data collection
KappaCCD
diffractometer
Absorption correction: Multi-scan
(SORTAV; Blessing, 1995, 1997)
Tmin = 0.963, Tmax = 0.971

10310 independent reflections

4898 reflections with I > 2(I)
Rint = 0.112

36207 measured reflections

Refinement
R[F2 > 2(F2)] = 0.062
2

606 parameters

wR(F ) = 0.162

H-atom parameters constrained

S = 0.93

max = 0.49 e 3

10310 reflections

min = 0.38 e 3

5-Cyano-4-(4-methoxyphenyl)-3,6-diphenyl-4,7-dihydro-2H-pyrazolo- [3,4-b]pyridine

CIF access
Crystal data
C26H20N4O

V = 4106.04 (13) 3

Mr = 404.46

Z=8

Monoclinic, C2/c

Mo K

a = 15.6264 (3)

= 0.08 mm1
T = 150.0 (1) K
0.15 0.15 0.12 mm

b = 12.4397 (2)
c = 21.1296 (4)
= 91.4371 (9)

Data collection
KappaCCD
diffractometer
Absorption correction: Multi-scan
(SORTAV; Blessing, 1995, 1997)
Tmin = 0.988, Tmax = 0.990

3620 independent reflections

3086 reflections with I > 2(I)
Rint = 0.072

48325 measured reflections

Refinement
R[F2 > 2(F2)] = 0.048

282 parameters

wR(F2) = 0.129

H-atom parameters constrained

S = 1.06

max = 0.39 e 3

3620 reflections

min = 0.34 e 3

3,4-Bis(4-chlorophenyl)-5-cyano-6-phenyl-1H-pyrazolo-[3,4-b]pyridine
Crystal data
C25H14Cl2N4

V = 2061.3 (3) 3

Mr = 441.30

Z=4

Monoclinic, P21/n

Mo K

a = 6.6222 (5)

= 0.34 mm1
T = 150.0 (1) K
0.10 0.10 0.05 mm

b = 11.0791 (10)
c = 28.264 (2)
= 96.248 (5)

Data collection
KappaCCD
diffractometer
Absorption correction: Multi-scan
(SORTAV; Blessing, 1995, 1997)
Tmin = 0.967, Tmax = 0.983
15117 measured reflections

4026 independent reflections

1975 reflections with I > 2(I)
Rint = 0.047

CIF access
Refinement
R[F2 > 2(F2)] = 0.058

280 parameters

wR(F2) = 0.115

H-atom parameters constrained

S = 0.94

max = 0.40 e 3

4026 reflections

min = 0.28 e 3

Acknowledgements
X-ray data were collected at the EPSRC, X-ray Crystallographic Service, University of Southampton, using a EnrafNonius
KappaCCD diffractometer. The authors thank the staff for all their help and advice.
References
Blessing, R. H. (1995). Acta Cryst. A51, 3338.
Blessing, R. H. (1997). J. Appl. Cryst. 30, 421426.
Ferguson, G. (1999). PRPKAPPA. A WORDPERFECT5.1 macro to formulate and polish CIF format files from the
SHELXL97 refinement of KappaCCD data. University of Guelph, Canada.
Johnson, C. K. (1976). ORTEPII. Report ORNL-5138. Oak Ridge National Laboratory, Tennessee, USA.
Nonius (1997). KappaCCD Server Software. Windows 3.11 Version. Nonius BV, Delft, The Netherlands.
Otwinowski, Z. & Minor, W. (1997). Methods Enzymol. 276, 307326.
Sheldrick, G. M. (1997a). SHELXS97. Program for the solution of crystal structures. University of Gttingen, Germany.
Sheldrick, G. M. (1997b). SHELXL97. Program for the refinement of crystal structures. University of Gttingen, Germany.
Spek, A. L. (1999). PLATON. Molecular Geometry and Graphics Program. January 1999 version. University of Utrecht,
The Netherlands.

CIF access
Scheme 1

supplementary materials

supplementary materials
4-(4-chlorophenyl)-5-cyano-3-(4-methylphenyl)-6-diphenyl-4,7-dihydro-2H-pyrazolo [3,4b]pyridine:dimethylformamide (2/1)
Crystal data
2C26H19ClN4C3H7NO

Z=2

Mr = 918.90

F000 = 960

Triclinic, P1

Dx = 1.314 Mg m3

a = 12.4124 (5)
b = 13.8275 (4)
c = 14.3744 (6)

Mo K radiation
= 0.71073
Cell parameters from 25 reflections
= 1.527.3

= 106.6376 (17)
= 99.610 (2)

= 0.19 mm1
T = 150.0 (1) K
Block, colourless

V = 2322.64 (15) 3

0.2 0.2 0.15 mm

= 91.747 (2)

Data collection
KappaCCD
diffractometer
Radiation source: fine-focus sealed X-ray tube

10310 independent reflections

Monochromator: graphite

4898 reflections with I > 2(I)

Rint = 0.112

T = 150.0(1) K

max = 27.3

scans and scans with offsets

min = 1.5

Absorption correction: Multi-scan

(SORTAV; Blessing, 1995, 1997)
Tmin = 0.963, Tmax = 0.971
36207 measured reflections

h = 1616
k = 1717
l = 1818

Refinement
Refinement on F2

Secondary atom site location: difference Fourier map

Least-squares matrix: full

Hydrogen site location: inferred from neighbouring

sites

R[F2 > 2(F2)] = 0.062

H-atom parameters constrained

wR(F2) = 0.162

w = 1/[2(Fo2) + (0.0726P)2]
where P = (Fo2 + 2Fc2)/3 ?

S = 0.93

(/)max = 0.002

10310 reflections

max = 0.49 e 3

606 parameters

min = 0.38 e 3

Primary atom site location: structure-invariant direct

Extinction correction: none
methods

sup-1

supplementary materials
Special details
Experimental. KappaCCD diffractometer using the following programs. Collect: Data collection software, Hooft, 1998 [Hooft, R.
(1998). Nonius BV, Delft, The Netherlands], is a graphical user interface written by EnrafNonius which encompasses the following
programs. DENZO (Otwinowski and Minor, 1997) and indexing and data collection software package and a scaling package, SCALEPACK both of which programs are produced by the company HKL. Absorption corrections are performed by the SORTAV package,
Blessing, 1995 and Blessing, 1997. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used.
No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental
table are calculated from the 'size' command in the SHELXL97 input file. Low temperature data is collected using an Oxford Cryosystems cryostream [Cosier, J. & Glazer, AM. (1986). J. Appl. Cryst. 19, 105107]. The Rint value for this compound is 0.112 which is
greater than 0.10. However, the R-factor for the "greater than" reflections is 0.0616 whereas that for all data is 0.1599 this suggests that
the high Rint results from discrepancies in the values of the weak reflections.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (2)
N11
N21
C31
C311
C321
C331
C341
C351
C361
C371
C7A1
C41
C411
C421
C431
C441
C451
C461
Cl41
C51
C511
N521
C61
C611
C621
C631
C641
C651
C661
C3A1
N71

sup-2

Uiso*/Ueq

0.31279 (19)
0.34303 (19)
0.4301 (2)
0.4732 (2)
0.5823 (2)
0.6213 (3)
0.5527 (3)
0.4443 (3)
0.4051 (3)
0.5969 (3)
0.3830 (2)
0.5465 (2)
0.5450 (2)
0.4438 (3)
0.4414 (3)
0.5417 (3)
0.6431 (3)
0.6446 (3)
0.53772 (9)
0.5276 (2)
0.6063 (3)
0.6725 (2)
0.4477 (3)
0.4243 (2)
0.4176 (3)
0.3888 (3)
0.3651 (3)
0.3701 (3)
0.4006 (3)
0.4588 (2)
0.3783 (2)

0.46649 (15)
0.55473 (15)
0.61564 (19)
0.71532 (19)
0.7640 (2)
0.8595 (2)
0.9095 (2)
0.8603 (2)
0.7650 (2)
1.0134 (2)
0.47397 (19)
0.58653 (18)
0.68439 (19)
0.7074 (2)
0.7963 (2)
0.8627 (2)
0.8425 (2)
0.7525 (2)
0.97578 (6)
0.5012 (2)
0.5127 (2)
0.52741 (19)
0.4178 (2)
0.3383 (2)
0.3599 (2)
0.2849 (2)
0.1881 (2)
0.1659 (2)
0.2402 (2)
0.56355 (19)
0.40074 (16)

0.07395 (18)
0.02102 (18)
0.0403 (2)
0.0082 (2)
0.0147 (2)
0.0555 (2)
0.0936 (2)
0.0891 (2)
0.0475 (2)
0.1392 (3)
0.1286 (2)
0.1661 (2)
0.2123 (2)
0.2688 (2)
0.3106 (2)
0.2946 (3)
0.2390 (3)
0.1981 (3)
0.34479 (8)
0.2427 (2)
0.2997 (2)
0.3417 (2)
0.2576 (2)
0.3364 (2)
0.4316 (2)
0.5055 (3)
0.4850 (3)
0.3912 (3)
0.3168 (2)
0.1120 (2)
0.19817 (18)

0.0280 (6)
0.0287 (6)
0.0262 (7)
0.0268 (7)
0.0316 (7)
0.0359 (8)
0.0338 (7)
0.0349 (8)
0.0322 (7)
0.0456 (9)
0.0278 (7)
0.0275 (7)
0.0280 (7)
0.0346 (8)
0.0390 (8)
0.0409 (9)
0.0447 (9)
0.0375 (8)
0.0637 (3)
0.0296 (7)
0.0332 (8)
0.0463 (8)
0.0299 (7)
0.0300 (7)
0.0351 (8)
0.0423 (8)
0.0427 (9)
0.0422 (9)
0.0377 (8)
0.0266 (7)
0.0305 (6)

supplementary materials
N12
N22
C32
C312
C322
C332
C342
C352
C362
C372
C3A2
C42
C412
C422
C432
C442
C452
C462
Cl42
C52
C512
N522
C62
C612
C622
C632
C642
C652
C662
N72
C7A2
O1
C1
N2
C3
C4
H21
H321
H331
H351
H361
H37A
H37B
H37C
H41
H421
H431
H451
H461

0.1797 (2)
0.1445 (2)
0.0585 (2)
0.0135 (2)
0.0825 (3)
0.0394 (3)
0.0738 (3)
0.1407 (3)
0.0989 (2)
0.1206 (3)
0.0344 (2)
0.0488 (2)
0.0381 (2)
0.0685 (3)
0.0807 (3)
0.0147 (3)
0.1220 (3)
0.1334 (3)
0.00113 (10)
0.0281 (2)
0.1041 (2)
0.1683 (2)
0.0518 (2)
0.0695 (2)
0.0679 (2)
0.0832 (3)
0.1025 (3)
0.1062 (3)
0.0894 (2)
0.12093 (19)
0.1117 (2)
0.2528 (2)
0.2233 (3)
0.2561 (2)
0.2105 (4)
0.3332 (4)
0.3101
0.6303
0.6944
0.3973
0.3321
0.6561
0.6272
0.5355
0.6223
0.3760
0.3728
0.7104
0.7137

0.51925 (15)
0.55577 (15)
0.49352 (19)
0.51872 (18)
0.5807 (2)
0.6072 (2)
0.5720 (2)
0.5088 (2)
0.48183 (19)
0.6026 (2)
0.41129 (18)
0.31540 (18)
0.26407 (18)
0.2586 (2)
0.2119 (2)
0.1707 (2)
0.1747 (2)
0.22141 (19)
0.11313 (6)
0.24955 (18)
0.1571 (2)
0.08371 (18)
0.27491 (18)
0.21027 (18)
0.11017 (19)
0.0522 (2)
0.0926 (2)
0.1925 (2)
0.2508 (2)
0.36584 (15)
0.43158 (18)
0.74772 (17)
0.8115 (3)
0.8325 (2)
0.9052 (4)
0.7776 (4)
0.5706
0.7317
0.8910
0.8921
0.7334
1.0441
1.0125
1.0499
0.5898
0.6624
0.8109
0.8881
0.7379

0.07986 (18)
0.15250 (18)
0.1717 (2)
0.2515 (2)
0.3328 (2)
0.4063 (2)
0.4034 (2)
0.3235 (2)
0.2487 (2)
0.4829 (2)
0.1070 (2)
0.0912 (2)
0.1852 (2)
0.2464 (2)
0.3319 (2)
0.3559 (2)
0.2960 (3)
0.2107 (2)
0.46311 (7)
0.0122 (2)
0.0123 (2)
0.0277 (2)
0.0354 (2)
0.1127 (2)
0.1040 (2)
0.1778 (2)
0.2588 (2)
0.2675 (2)
0.1952 (2)
0.01714 (18)
0.0537 (2)
0.2201 (2)
0.2624 (3)
0.3582 (2)
0.4003 (5)
0.4202 (4)
0.0208
0.0088
0.0577
0.1146
0.0455
0.1132
0.2085
0.1248
0.1194
0.2791
0.3489
0.2284
0.1608

0.0282 (6)
0.0295 (6)
0.0263 (7)
0.0257 (7)
0.0310 (7)
0.0339 (8)
0.0310 (7)
0.0333 (8)
0.0300 (7)
0.0425 (9)
0.0251 (7)
0.0242 (7)
0.0244 (7)
0.0327 (7)
0.0400 (8)
0.0379 (8)
0.0396 (8)
0.0321 (7)
0.0646 (3)
0.0244 (7)
0.0277 (7)
0.0382 (7)
0.0252 (7)
0.0251 (7)
0.0302 (7)
0.0360 (8)
0.0395 (8)
0.0368 (8)
0.0308 (7)
0.0289 (6)
0.0255 (7)
0.0687 (8)
0.0577 (10)
0.0507 (8)
0.131 (3)
0.0940 (16)
0.034*
0.038*
0.043*
0.042*
0.039*
0.068*
0.068*
0.068*
0.033*
0.042*
0.047*
0.054*
0.045*

sup-3

supplementary materials
H621
H631
H641
H651
H661
H71
H22
H322
H332
H352
H362
H37D
H37E
H37F
H42
H422
H432
H452
H462
H622
H632
H642
H652
H662
H72
H1
H3A
H3B
H3C
H4A
H4B
H4C

0.4325
0.3855
0.3456
0.3530
0.4052
0.3326
0.1738
0.1586
0.0869
0.2162
0.1462
0.1440
0.0626
0.1853
0.1266
0.1334
0.1531
0.1866
0.2060
0.0566
0.0803
0.1132
0.1200
0.0914
0.1693
0.1739
0.1678
0.2720
0.1611
0.3660
0.2918
0.3929

0.4251
0.2998
0.1379
0.1006
0.2246
0.3453
0.6127
0.6045
0.6495
0.4835
0.4389
0.6650
0.6081
0.5541
0.3291
0.2869
0.2086
0.1463
0.2241
0.0822
0.0150
0.0530
0.2203
0.3178
0.3819
0.8485
0.9396
0.9512
0.8738
0.7407
0.7332
0.8223

0.4457
0.5688
0.5346
0.3779
0.2534
0.2042
0.1833
0.3373
0.4591
0.3199
0.1964
0.4711
0.5445
0.4840
0.0673
0.2301
0.3724
0.3126
0.1702
0.0487
0.1724
0.3077
0.3221
0.2015
0.0491
0.2246
0.3496
0.4441
0.4355
0.3813
0.4535
0.4671

0.042*
0.051*
0.051*
0.051*
0.045*
0.037*
0.035*
0.037*
0.041*
0.040*
0.036*
0.064*
0.064*
0.064*
0.029*
0.039*
0.048*
0.048*
0.039*
0.036*
0.043*
0.047*
0.044*
0.037*
0.035*
0.069*
0.196*
0.196*
0.196*
0.141*
0.141*
0.141*

Atomic displacement parameters (2)

N11
N21
C31
C311
C321
C331
C341
C351
C361
C371
C7A1
C41

sup-4

U11
0.0314 (15)
0.0318 (14)
0.0247 (16)
0.0305 (17)
0.0278 (18)
0.0325 (18)
0.0393 (19)
0.0367 (19)
0.0280 (17)
0.053 (2)
0.0319 (18)
0.0275 (17)

U22
0.0279 (13)
0.0292 (13)
0.0281 (15)
0.0265 (15)
0.0361 (17)
0.0355 (17)
0.0320 (16)
0.0334 (17)
0.0362 (17)
0.0333 (17)
0.0296 (16)
0.0287 (15)

U33
0.0242 (15)
0.0264 (16)
0.0246 (18)
0.0221 (18)
0.029 (2)
0.035 (2)
0.027 (2)
0.037 (2)
0.031 (2)
0.046 (2)
0.0240 (19)
0.0272 (19)

U12
0.0022 (11)
0.0034 (11)
0.0018 (13)
0.0028 (13)
0.0032 (14)
0.0074 (14)
0.0026 (14)
0.0069 (14)
0.0018 (14)
0.0018 (15)
0.0098 (13)
0.0039 (13)

U13
0.0092 (13)
0.0123 (13)
0.0068 (14)
0.0071 (14)
0.0080 (15)
0.0101 (16)
0.0075 (16)
0.0147 (17)
0.0098 (16)
0.0146 (19)
0.0086 (15)
0.0100 (15)

U23
0.0005 (11)
0.0011 (11)
0.0064 (13)
0.0037 (13)
0.0016 (14)
0.0002 (15)
0.0007 (14)
0.0005 (14)
0.0017 (14)
0.0071 (16)
0.0067 (13)
0.0032 (13)

supplementary materials
C411
C421
C431
C441
C451
C461
Cl41
C51
C511
N521
C61
C611
C621
C631
C641
C651
C661
C3A1
N71
N12
N22
C32
C312
C322
C332
C342
C352
C362
C372
C3A2
C42
C412
C422
C432
C442
C452
C462
Cl42
C52
C512
N522
C62
C612
C622
C632
C642
C652
C662
N72

0.0343 (18)
0.0341 (19)
0.043 (2)
0.058 (2)
0.050 (2)
0.0355 (19)
0.0933 (8)
0.0339 (18)
0.0375 (19)
0.0484 (19)
0.0363 (18)
0.0336 (18)
0.042 (2)
0.052 (2)
0.053 (2)
0.053 (2)
0.050 (2)
0.0299 (17)
0.0418 (16)
0.0345 (15)
0.0385 (15)
0.0280 (17)
0.0305 (18)
0.0298 (17)
0.039 (2)
0.0371 (19)
0.0301 (18)
0.0354 (19)
0.055 (2)
0.0284 (17)
0.0253 (16)
0.0291 (17)
0.0335 (19)
0.044 (2)
0.060 (2)
0.050 (2)
0.0324 (18)
0.1069 (8)
0.0259 (16)
0.0314 (18)
0.0399 (16)
0.0306 (17)
0.0251 (16)
0.0349 (18)
0.044 (2)
0.053 (2)
0.047 (2)
0.0371 (18)
0.0340 (15)

0.0283 (15)
0.0318 (16)
0.0388 (18)
0.0267 (16)
0.0313 (17)
0.0359 (17)
0.0334 (5)
0.0317 (16)
0.0290 (16)
0.0501 (17)
0.0284 (16)
0.0298 (16)
0.0329 (16)
0.044 (2)
0.0384 (19)
0.0287 (17)
0.0342 (17)
0.0261 (15)
0.0231 (12)
0.0236 (12)
0.0218 (12)
0.0227 (14)
0.0202 (14)
0.0336 (16)
0.0302 (16)
0.0272 (15)
0.0308 (16)
0.0232 (14)
0.0413 (18)
0.0213 (14)
0.0241 (14)
0.0187 (13)
0.0352 (16)
0.0373 (17)
0.0249 (16)
0.0310 (16)
0.0270 (15)
0.0481 (5)
0.0227 (14)
0.0283 (16)
0.0302 (14)
0.0202 (14)
0.0225 (14)
0.0266 (15)
0.0240 (15)
0.0346 (18)
0.0358 (17)
0.0247 (15)
0.0244 (12)

0.0264 (19)
0.037 (2)
0.040 (2)
0.050 (2)
0.058 (3)
0.044 (2)
0.0865 (9)
0.028 (2)
0.035 (2)
0.051 (2)
0.028 (2)
0.031 (2)
0.033 (2)
0.032 (2)
0.037 (2)
0.044 (2)
0.035 (2)
0.0243 (19)
0.0279 (16)
0.0277 (16)
0.0297 (16)
0.0309 (19)
0.0282 (19)
0.031 (2)
0.030 (2)
0.033 (2)
0.043 (2)
0.032 (2)
0.039 (2)
0.0271 (19)
0.0243 (18)
0.0270 (19)
0.032 (2)
0.036 (2)
0.028 (2)
0.040 (2)
0.036 (2)
0.0314 (6)
0.0227 (18)
0.0267 (19)
0.045 (2)
0.0234 (18)
0.0254 (18)
0.032 (2)
0.039 (2)
0.033 (2)
0.029 (2)
0.029 (2)
0.0300 (16)

0.0045 (13)
0.0002 (14)
0.0116 (16)
0.0115 (16)
0.0049 (16)
0.0044 (15)
0.0203 (5)
0.0095 (14)
0.0112 (14)
0.0153 (14)
0.0121 (14)
0.0125 (13)
0.0099 (14)
0.0140 (17)
0.0117 (16)
0.0104 (15)
0.0160 (15)
0.0054 (13)
0.0016 (11)
0.0025 (11)
0.0032 (11)
0.0067 (13)
0.0050 (13)
0.0042 (13)
0.0021 (14)
0.0079 (14)
0.0079 (14)
0.0052 (13)
0.0150 (16)
0.0052 (12)
0.0055 (12)
0.0028 (12)
0.0053 (14)
0.0100 (15)
0.0002 (15)
0.0065 (15)
0.0013 (13)
0.0044 (5)
0.0014 (12)
0.0084 (14)
0.0010 (13)
0.0048 (12)
0.0023 (12)
0.0048 (13)
0.0076 (14)
0.0082 (15)
0.0062 (15)
0.0039 (13)
0.0019 (11)

0.0175 (16)
0.0124 (17)
0.0169 (18)
0.033 (2)
0.031 (2)
0.0172 (17)
0.0543 (7)
0.0137 (16)
0.0104 (17)
0.0272 (17)
0.0104 (16)
0.0131 (15)
0.0138 (17)
0.0123 (18)
0.0135 (19)
0.0112 (19)
0.0156 (18)
0.0081 (15)
0.0151 (13)
0.0129 (13)
0.0145 (13)
0.0114 (15)
0.0111 (15)
0.0125 (16)
0.0100 (16)
0.0162 (17)
0.0164 (17)
0.0106 (16)
0.0225 (19)
0.0098 (14)
0.0086 (14)
0.0121 (15)
0.0145 (16)
0.0067 (17)
0.0165 (19)
0.025 (2)
0.0123 (16)
0.0186 (6)
0.0058 (14)
0.0119 (15)
0.0161 (15)
0.0055 (15)
0.0055 (14)
0.0138 (16)
0.0107 (17)
0.0160 (18)
0.0152 (17)
0.0092 (16)
0.0162 (13)

0.0024 (13)
0.0035 (14)
0.0096 (16)
0.0051 (15)
0.0027 (16)
0.0054 (15)
0.0227 (5)
0.0088 (14)
0.0039 (14)
0.0123 (15)
0.0061 (14)
0.0058 (14)
0.0034 (15)
0.0025 (16)
0.0102 (16)
0.0009 (16)
0.0067 (15)
0.0050 (13)
0.0004 (11)
0.0009 (11)
0.0024 (11)
0.0057 (13)
0.0033 (13)
0.0018 (14)
0.0052 (14)
0.0030 (14)
0.0075 (15)
0.0009 (13)
0.0032 (16)
0.0052 (13)
0.0018 (12)
0.0000 (12)
0.0077 (14)
0.0069 (16)
0.0061 (14)
0.0009 (15)
0.0008 (14)
0.0122 (4)
0.0027 (12)
0.0048 (13)
0.0019 (12)
0.0026 (12)
0.0003 (12)
0.0064 (14)
0.0007 (14)
0.0036 (15)
0.0016 (15)
0.0019 (13)
0.0005 (11)

sup-5

supplementary materials
C7A2
O1
C1
N2
C3
C4

0.0310 (17)
0.088 (2)
0.056 (3)
0.0447 (18)
0.086 (4)
0.063 (3)

0.0190 (14)
0.0402 (14)
0.048 (2)
0.0542 (18)
0.111 (4)
0.125 (4)

0.0265 (19)
0.077 (2)
0.053 (3)
0.047 (2)
0.200 (7)
0.068 (4)

0.0041 (12)
0.0195 (13)
0.0123 (19)
0.0060 (14)
0.023 (3)
0.016 (3)

0.0090 (15)
0.0438 (19)
0.003 (2)
0.0138 (17)
0.082 (5)
0.005 (3)

0.0019 (12)
0.0199 (14)
0.006 (2)
0.0143 (16)
0.078 (4)
0.027 (3)

Geometric parameters (, )
N11C7A1
N11N21
N21C31
C31C3A1
C31C311
C311C321
C311C361
C321C331
C331C341
C341C351
C341C371
C351C361
C7A1N71
C7A1C3A1
C41C3A1
C41C411
C41C51
C411C421
C411C461
C421C431
C431C441
C441C451
C441Cl41
C451C461
C51C61
C51C511
C511N521
C61N71
C61C611
C611C621
C611C661
C621C631
C631C641
C641C651
C651C661
N12C7A2
N12N22

1.324 (3)
1.355 (3)
1.355 (3)
1.399 (4)
1.468 (4)
1.384 (4)
1.397 (4)
1.377 (4)
1.393 (4)
1.386 (4)
1.506 (4)
1.379 (4)
1.384 (4)
1.393 (4)
1.508 (4)
1.526 (3)
1.530 (4)
1.380 (4)
1.383 (4)
1.386 (4)
1.374 (4)
1.363 (5)
1.744 (3)
1.393 (4)
1.358 (4)
1.437 (4)
1.148 (3)
1.375 (3)
1.485 (4)
1.391 (4)
1.395 (4)
1.387 (4)
1.381 (4)
1.378 (5)
1.384 (4)
1.332 (3)
1.356 (3)

N22C32
C32C3A2
C32C312
C312C362
C312C322
C322C332
C332C342
C342C352
C342C372
C352C362
C3A2C7A2
C3A2C42
C42C412
C42C52
C412C422
C412C462
C422C432
C432C442
C442C452
C442Cl42
C452C462
C52C62
C52C512
C512N522
C62N72
C62C612
C612C622
C612C662
C622C632
C632C642
C642C652
C652C662
N72C7A2
O1C1
C1N2
N2C3
N2C4

1.353 (3)
1.382 (4)
1.469 (4)
1.392 (4)
1.398 (4)
1.380 (4)
1.397 (4)
1.387 (4)
1.502 (4)
1.386 (4)
1.389 (4)
1.505 (4)
1.527 (4)
1.539 (4)
1.379 (4)
1.382 (4)
1.388 (4)
1.366 (4)
1.375 (5)
1.732 (3)
1.385 (4)
1.365 (4)
1.424 (4)
1.153 (3)
1.370 (3)
1.491 (4)
1.391 (3)
1.394 (4)
1.386 (4)
1.371 (4)
1.386 (4)
1.380 (4)
1.387 (3)
1.218 (4)
1.327 (5)
1.431 (5)
1.442 (5)

C7A1N11N21
N11N21C31
N21C31C3A1

103.1 (2)
113.6 (2)
105.7 (2)

N22C32C3A2
N22C32C312
C3A2C32C312

106.2 (2)
120.8 (3)
133.0 (3)

sup-6

supplementary materials
N21C31C311
C3A1C31C311
C321C311C361
C321C311C31
C361C311C31
C331C321C311
C321C331C341
C351C341C331
C351C341C371
C331C341C371
C361C351C341
C351C361C311
N11C7A1N71
N11C7A1C3A1
N71C7A1C3A1
C3A1C41C411
C3A1C41C51
C411C41C51
C421C411C461
C421C411C41
C461C411C41
C411C421C431
C441C431C421
C451C441C431
C451C441Cl41
C431C441Cl41
C441C451C461
C411C461C451
C61C51C511
C61C51C41
C511C51C41
N521C511C51
C51C61N71
C51C61C611
N71C61C611
C621C611C661
C621C611C61
C661C611C61
C631C621C611
C641C631C621
C651C641C631
C641C651C661
C651C661C611
C7A1C3A1C31
C7A1C3A1C41
C31C3A1C41
C61N71C7A1
C7A2N12N22
C32N22N12

121.6 (2)
132.7 (2)
117.7 (3)
121.0 (2)
121.3 (3)
121.3 (3)
121.0 (3)
118.0 (3)
121.6 (3)
120.4 (3)
121.0 (3)
121.0 (3)
122.8 (2)
113.8 (3)
123.3 (3)
113.6 (2)
108.4 (2)
111.1 (2)
118.3 (3)
120.7 (3)
121.0 (3)
121.1 (3)
119.2 (3)
121.2 (3)
119.8 (3)
119.0 (3)
119.1 (3)
121.1 (3)
119.6 (3)
125.8 (3)
114.5 (2)
175.7 (3)
120.8 (3)
125.6 (3)
113.6 (2)
118.9 (3)
121.2 (2)
119.7 (3)
120.5 (3)
119.9 (3)
120.2 (3)
120.2 (3)
120.3 (3)
103.8 (2)
122.2 (3)
134.0 (2)
119.1 (2)
102.9 (2)
113.2 (2)

C362C312C322
C362C312C32
C322C312C32
C332C322C312
C322C332C342
C352C342C332
C352C342C372
C332C342C372
C362C352C342
C352C362C312
C32C3A2C7A2
C32C3A2C42
C7A2C3A2C42
C3A2C42C412
C3A2C42C52
C412C42C52
C422C412C462
C422C412C42
C462C412C42
C412C422C432
C442C432C422
C432C442C452
C432C442Cl42
C452C442Cl42
C442C452C462
C412C462C452
C62C52C512
C62C52C42
C512C52C42
N522C512C52
C52C62N72
C52C62C612
N72C62C612
C622C612C662
C622C612C62
C662C612C62
C632C622C612
C642C632C622
C632C642C652
C662C652C642
C652C662C612
C62N72C7A2
N12C7A2N72
N12C7A2C3A2
N72C7A2C3A2
O1C1N2
C1N2C3
C1N2C4
C3N2C4

117.9 (3)
121.2 (3)
120.9 (3)
121.1 (3)
121.4 (3)
116.9 (3)
121.9 (3)
121.1 (3)
122.3 (3)
120.3 (3)
104.2 (2)
133.3 (3)
122.5 (2)
112.0 (2)
108.3 (2)
111.1 (2)
118.4 (3)
120.0 (2)
121.6 (3)
121.2 (3)
119.3 (3)
120.6 (3)
119.1 (3)
120.3 (2)
119.6 (3)
120.8 (3)
120.4 (3)
125.4 (2)
114.2 (2)
175.8 (3)
121.3 (2)
124.4 (2)
114.3 (2)
118.9 (3)
121.5 (2)
119.6 (2)
119.9 (3)
120.8 (3)
119.8 (3)
119.9 (3)
120.6 (3)
118.9 (2)
122.8 (2)
113.5 (2)
123.7 (2)
125.2 (4)
120.3 (4)
119.5 (3)
120.0 (4)

sup-7

supplementary materials
C7A1N11N21C31
N11N21C31C3A1
N11N21C31C311
N21C31C311C321
C3A1C31C311C321
N21C31C311C361
C3A1C31C311C361
C361C311C321C331
C31C311C321C331
C311C321C331C341
C321C331C341C351
C321C331C341C371
C331C341C351C361
C371C341C351C361
C341C351C361C311
C321C311C361C351
C31C311C361C351
N21N11C7A1N71
N21N11C7A1C3A1
C3A1C41C411C421
C51C41C411C421
C3A1C41C411C461
C51C41C411C461
C461C411C421C431
C41C411C421C431
C411C421C431C441
C421C431C441C451
C421C431C441Cl41
C431C441C451C461
Cl41C441C451C461
C421C411C461C451
C41C411C461C451
C441C451C461C411
C3A1C41C51C61
C411C41C51C61
C3A1C41C51C511
C411C41C51C511
C61C51C511N521
C41C51C511N521
C511C51C61N71
C41C51C61N71
C511C51C61C611
C41C51C61C611
C51C61C611C621
N71C61C611C621
C51C61C611C661
N71C61C611C661
C661C611C621C631
C61C611C621C631

sup-8

0.7 (3)
0.4 (3)
178.6 (2)
157.9 (3)
24.4 (5)
23.5 (4)
154.3 (3)
2.2 (4)
176.5 (3)
1.4 (5)
0.0 (5)
179.2 (3)
0.6 (5)
179.7 (3)
0.3 (5)
1.6 (4)
177.1 (3)
176.9 (2)
0.8 (3)
49.6 (4)
72.9 (3)
130.0 (3)
107.5 (3)
0.0 (4)
179.6 (3)
0.5 (5)
0.3 (5)
178.4 (2)
0.3 (5)
179.0 (2)
0.6 (5)
179.0 (3)
0.8 (5)
1.7 (4)
127.2 (3)
179.5 (2)
55.0 (3)
176 (4)
2(4)
173.9 (2)
3.7 (5)
6.9 (5)
175.5 (3)
44.1 (4)
135.2 (3)
140.6 (3)
40.1 (4)
0.6 (4)
176.0 (3)

N12N22C32C3A2
N12N22C32C312
N22C32C312C362
C3A2C32C312C362
N22C32C312C322
C3A2C32C312C322
C362C312C322C332
C32C312C322C332
C312C322C332C342
C322C332C342C352
C322C332C342C372
C332C342C352C362
C372C342C352C362
C342C352C362C312
C322C312C362C352
C32C312C362C352
N22C32C3A2C7A2
C312C32C3A2C7A2
N22C32C3A2C42
C312C32C3A2C42
C32C3A2C42C412
C7A2C3A2C42C412
C32C3A2C42C52
C7A2C3A2C42C52
C3A2C42C412C422
C52C42C412C422
C3A2C42C412C462
C52C42C412C462
C462C412C422C432
C42C412C422C432
C412C422C432C442
C422C432C442C452
C422C432C442Cl42
C432C442C452C462
Cl42C442C452C462
C422C412C462C452
C42C412C462C452
C442C452C462C412
C3A2C42C52C62
C412C42C52C62
C3A2C42C52C512
C412C42C52C512
C62C52C512N522
C42C52C512N522
C512C52C62N72
C42C52C62N72
C512C52C62C612
C42C52C62C612
C52C62C612C622

0.8 (3)
176.9 (2)
152.4 (3)
30.6 (5)
27.6 (4)
149.4 (3)
2.2 (4)
177.8 (2)
1.1 (4)
0.4 (4)
179.0 (3)
0.8 (4)
178.6 (3)
0.4 (4)
1.8 (4)
178.2 (2)
0.8 (3)
176.5 (3)
178.4 (3)
1.1 (6)
52.7 (4)
124.5 (3)
175.6 (3)
1.7 (4)
44.2 (3)
77.1 (3)
136.4 (3)
102.3 (3)
0.2 (4)
179.6 (3)
0.2 (5)
0.4 (5)
179.5 (2)
0.3 (5)
179.6 (2)
0.3 (4)
179.7 (3)
0.1 (4)
0.4 (4)
123.9 (3)
178.0 (2)
58.5 (3)
177 (4)
5(4)
175.9 (3)
1.5 (4)
1.8 (4)
179.2 (3)
42.1 (4)

supplementary materials
C611C621C631C641
C621C631C641C651
C631C641C651C661
C641C651C661C611
C621C611C661C651
C61C611C661C651
N11C7A1C3A1C31
N71C7A1C3A1C31
N11C7A1C3A1C41
N71C7A1C3A1C41
N21C31C3A1C7A1
C311C31C3A1C7A1
N21C31C3A1C41
C311C31C3A1C41
C411C41C3A1C7A1
C51C41C3A1C7A1
C411C41C3A1C31
C51C41C3A1C31
C51C61N71C7A1
C611C61N71C7A1
N11C7A1N71C61
C3A1C7A1N71C61
C7A2N12N22C32

0.9 (5)
0.1 (5)
0.9 (5)
1.2 (5)
0.4 (4)
175.0 (3)
0.6 (3)
177.1 (3)
179.5 (2)
2.8 (4)
0.2 (3)
177.9 (3)
180.0 (3)
2.0 (6)
128.8 (3)
4.8 (4)
51.1 (4)
175.0 (3)
6.2 (4)
173.1 (2)
174.4 (3)
3.1 (4)
0.4 (3)

N72C62C612C622
C52C62C612C662
N72C62C612C662
C662C612C622C632
C62C612C622C632
C612C622C632C642
C622C632C642C652
C632C642C652C662
C642C652C662C612
C622C612C662C652
C62C612C662C652
C52C62N72C7A2
C612C62N72C7A2
N22N12C7A2N72
N22N12C7A2C3A2
C62N72C7A2N12
C62N72C7A2C3A2
C32C3A2C7A2N12
C42C3A2C7A2N12
C32C3A2C7A2N72
C42C3A2C7A2N72
O1C1N2C3
O1C1N2C4

140.1 (3)
138.7 (3)
39.2 (4)
1.6 (4)
179.2 (3)
1.5 (5)
0.4 (5)
0.6 (5)
0.5 (5)
0.6 (4)
179.8 (3)
2.3 (4)
179.8 (2)
177.4 (2)
0.1 (3)
176.2 (3)
1.1 (4)
0.6 (3)
178.5 (3)
176.9 (3)
1.0 (4)
176.2 (4)
0.3 (5)

Hydrogen-bond geometry (, )
DHA
N21H21N12
N22H22O1
N72H72N11

DH
0.88
0.88
0.88

HA
2.05
1.92
2.07

DA
2.801 (4)
2.775 (3)
2.889 (3)

DHA
142
164
155

5-Cyano-4-(4-methoxyphenyl)-3,6-diphenyl-4,7-dihydro-2H-pyrazolo- [3,4-b]pyridine
Crystal data
C26H20N4O

F000 = 1696

Mr = 404.46

Dx = 1.309 Mg m3

Monoclinic, C2/c
a = 15.6264 (3)
b = 12.4397 (2)
c = 21.1296 (4)
= 91.4371 (9)
V = 4106.04 (13) 3
Z=8

Mo K radiation
= 0.71073
Cell parameters from 3620 reflections
= 1.925.0
= 0.08 mm1
T = 150.0 (1) K
Block, colourless
0.15 0.15 0.12 mm

sup-9

supplementary materials
Data collection
KappaCCD
diffractometer
Radiation source: fine-focus sealed X-ray tube

3620 independent reflections

Monochromator: graphite

3086 reflections with I > 2(I)

Rint = 0.072

T = 150.0(1) K

max = 25.0

scans and scans with offsets

min = 1.9

Absorption correction: Multi-scan

(SORTAV; Blessing, 1995, 1997)
Tmin = 0.988, Tmax = 0.990

h = 1818
k = 1414
l = 2525

48325 measured reflections

Refinement
Hydrogen site location: inferred from neighbouring
sites
H-atom parameters constrained

Refinement on F2
Least-squares matrix: full

w = 1/[2(Fo2) + (0.0653P)2 + 4.5942P]

R[F2 > 2(F2)] = 0.048

where P = (Fo2 + 2Fc2)/3 ?

wR(F2) = 0.129

(/)max < 0.001

S = 1.06

max = 0.39 e 3

3620 reflections

min = 0.34 e 3

282 parameters

Extinction correction: SHELXL,

Fc*=kFc[1+0.001xFc23/sin(2)]-1/4

Primary atom site location: structure-invariant direct

Extinction coefficient: 0.0026 (4)
methods
Secondary atom site location: difference Fourier map

Special details
Experimental. KappaCCD diffractometer using the following programs. Collect: Data collection software, Hooft, 1998 [Hooft, R.
(1998). Nonius BV, Delft, The Netherlands], is a graphical user interface written by EnrafNonius which encompasses the following
programs. DENZO (Otwinowski and Minor, 1997) and indexing and data collection software package and a scaling package, SCALEPACK both of which programs are produced by the company HKL. Absorption corrections are performed by the SORTAV package,
Blessing, 1995 and Blessing, 1997. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used.
No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental
table are calculated from the 'size' command in the SHELXL97 input file. Low temperature data is collected using an Oxford Cryosystems cryostream [Cosier, J. & Glazer, AM. (1986). J. Appl. Cryst. 19, 105107].

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (2)
N1
N2
C3
C3A

sup-10

Uiso*/Ueq

0.05038 (9)
0.10589 (9)
0.08061 (11)
0.00281 (11)

0.10626 (12)
0.07969 (12)
0.00627 (13)
0.03923 (13)

0.16622 (7)
0.12000 (7)
0.08468 (8)
0.10912 (8)

0.0279 (4)
0.0272 (4)
0.0236 (4)
0.0225 (4)

supplementary materials
C4
C5
C6
C7A
N7
C31
C32
C33
C34
C35
C36
C41
C42
C43
C44
C45
C46
O47
C48
C51
N52
C61
C62
C63
C64
C65
C66
H2
H4
H7
H32
H33
H34
H35
H36
H42
H43
H45
H46
H48A
H48B
H48C
H62
H63
H64
H65
H66

0.06074 (11)
0.13673 (10)
0.14105 (10)
0.01115 (11)
0.08121 (9)
0.13386 (11)
0.21403 (12)
0.26367 (13)
0.23519 (14)
0.15542 (15)
0.10469 (13)
0.02806 (10)
0.02465 (11)
0.04698 (12)
0.01464 (11)
0.03834 (12)
0.05916 (12)
0.03091 (9)
0.07374 (15)
0.20549 (11)
0.25826 (10)
0.20774 (11)
0.22894 (12)
0.29080 (13)
0.33126 (12)
0.30997 (12)
0.24844 (12)
0.1526
0.0817
0.0869
0.2345
0.3165
0.2695
0.1355
0.0504
0.0458
0.0830
0.0601
0.0944
0.0451
0.0733
0.1318
0.2012
0.3053
0.3727
0.3370
0.2342

0.12643 (13)
0.11692 (13)
0.04971 (13)
0.03307 (14)
0.02914 (12)
0.04772 (14)
0.00425 (18)
0.0443 (2)
0.1301 (2)
0.17275 (18)
0.13157 (16)
0.24127 (14)
0.27541 (15)
0.38353 (15)
0.45741 (14)
0.42462 (15)
0.31775 (15)
0.56606 (10)
0.60698 (18)
0.18912 (14)
0.24966 (13)
0.05716 (13)
0.15675 (14)
0.16498 (16)
0.07385 (16)
0.02564 (16)
0.03420 (15)
0.1142
0.1140
0.0752
0.0525
0.0133
0.1587
0.2298
0.1601
0.2256
0.4057
0.4747
0.2960
0.5827
0.6841
0.5818
0.2183
0.2321
0.0796
0.0870
0.1015

0.09207 (8)
0.13635 (8)
0.18704 (8)
0.15827 (8)
0.19728 (7)
0.03369 (8)
0.02201 (9)
0.02583 (10)
0.06221 (10)
0.05173 (10)
0.00493 (9)
0.09683 (8)
0.14594 (9)
0.15271 (9)
0.10912 (9)
0.05997 (9)
0.05342 (9)
0.11148 (7)
0.16637 (12)
0.12249 (8)
0.10814 (8)
0.23547 (8)
0.26054 (9)
0.30584 (9)
0.32766 (9)
0.30391 (9)
0.25812 (9)
0.1138
0.0486
0.2272
0.0467
0.0336
0.0934
0.0764
0.0009
0.1752
0.1859
0.0311
0.0197
0.2034
0.1651
0.1677
0.2467
0.3217
0.3583
0.3187
0.2424

0.0228 (4)
0.0227 (4)
0.0231 (4)
0.0241 (4)
0.0270 (4)
0.0250 (4)
0.0372 (5)
0.0464 (6)
0.0435 (5)
0.0447 (5)
0.0360 (5)
0.0237 (4)
0.0305 (4)
0.0339 (5)
0.0290 (4)
0.0319 (4)
0.0294 (4)
0.0394 (4)
0.0491 (6)
0.0255 (4)
0.0342 (4)
0.0246 (4)
0.0302 (4)
0.0366 (5)
0.0351 (5)
0.0337 (4)
0.0309 (4)
0.033*
0.027*
0.032*
0.045*
0.056*
0.052*
0.054*
0.043*
0.037*
0.041*
0.038*
0.035*
0.074*
0.074*
0.074*
0.036*
0.044*
0.042*
0.040*
0.037*

sup-11

supplementary materials
Atomic displacement parameters (2)
N1
N2
C3
C3A
C4
C5
C6
C7A
N7
C31
C32
C33
C34
C35
C36
C41
C42
C43
C44
C45
C46
O47
C48
C51
N52
C61
C62
C63
C64
C65
C66

U11
0.0238 (8)
0.0216 (7)
0.0217 (8)
0.0219 (9)
0.0219 (9)
0.0192 (8)
0.0171 (8)
0.0201 (8)
0.0233 (8)
0.0228 (9)
0.0253 (10)
0.0233 (10)
0.0369 (11)
0.0523 (13)
0.0375 (11)
0.0194 (8)
0.0266 (9)
0.0274 (10)
0.0242 (9)
0.0297 (10)
0.0292 (10)
0.0382 (8)
0.0443 (13)
0.0219 (9)
0.0258 (8)
0.0179 (8)
0.0301 (10)
0.0395 (11)
0.0306 (10)
0.0262 (9)
0.0273 (9)

U22
0.0259 (8)
0.0255 (8)
0.0216 (8)
0.0194 (8)
0.0215 (9)
0.0187 (8)
0.0198 (8)
0.0222 (9)
0.0255 (8)
0.0270 (9)
0.0525 (13)
0.0774 (16)
0.0624 (14)
0.0440 (12)
0.0366 (11)
0.0229 (9)
0.0256 (9)
0.0341 (11)
0.0225 (9)
0.0302 (10)
0.0295 (10)
0.0251 (7)
0.0356 (12)
0.0232 (9)
0.0305 (9)
0.0242 (9)
0.0256 (9)
0.0313 (10)
0.0393 (11)
0.0312 (10)
0.0225 (9)

U33
0.0342 (8)
0.0347 (8)
0.0274 (9)
0.0264 (9)
0.0249 (9)
0.0302 (9)
0.0324 (9)
0.0300 (9)
0.0325 (8)
0.0252 (9)
0.0340 (11)
0.0388 (12)
0.0318 (11)
0.0383 (12)
0.0344 (11)
0.0289 (9)
0.0393 (11)
0.0399 (11)
0.0406 (11)
0.0360 (10)
0.0297 (9)
0.0550 (9)
0.0672 (15)
0.0316 (9)
0.0466 (10)
0.0316 (9)
0.0354 (10)
0.0397 (11)
0.0358 (11)
0.0439 (11)
0.0431 (11)

U12
0.0063 (6)
0.0076 (6)
0.0027 (7)
0.0024 (7)
0.0036 (7)
0.0018 (7)
0.0006 (6)
0.0024 (7)
0.0064 (6)
0.0005 (7)
0.0083 (9)
0.0082 (10)
0.0011 (10)
0.0105 (10)
0.0116 (9)
0.0032 (7)
0.0031 (7)
0.0031 (8)
0.0027 (7)
0.0045 (8)
0.0025 (8)
0.0039 (6)
0.0100 (10)
0.0001 (8)
0.0075 (7)
0.0008 (7)
0.0059 (8)
0.0032 (9)
0.0015 (9)
0.0029 (8)
0.0029 (7)

U13
0.0051 (6)
0.0056 (6)
0.0003 (7)
0.0012 (7)
0.0004 (7)
0.0015 (7)
0.0012 (7)
0.0021 (7)
0.0060 (6)
0.0013 (7)
0.0024 (8)
0.0057 (8)
0.0087 (9)
0.0146 (10)
0.0113 (8)
0.0071 (7)
0.0012 (8)
0.0031 (8)
0.0095 (8)
0.0043 (8)
0.0045 (7)
0.0009 (7)
0.0056 (11)
0.0043 (7)
0.0054 (7)
0.0000 (7)
0.0076 (8)
0.0125 (9)
0.0108 (8)
0.0058 (8)
0.0041 (8)

U23
0.0033 (6)
0.0012 (6)
0.0030 (7)
0.0025 (7)
0.0004 (7)
0.0020 (7)
0.0022 (7)
0.0006 (7)
0.0073 (6)
0.0056 (7)
0.0070 (9)
0.0066 (11)
0.0052 (10)
0.0085 (9)
0.0024 (8)
0.0004 (7)
0.0023 (8)
0.0002 (8)
0.0051 (8)
0.0089 (8)
0.0035 (7)
0.0036 (6)
0.0065 (10)
0.0004 (7)
0.0052 (7)
0.0016 (7)
0.0031 (7)
0.0068 (8)
0.0011 (8)
0.0089 (8)
0.0042 (8)

Geometric parameters (, )
N1C7A
N1N2
N2C3
C3C3A
C3C31
C3AC7A
C3AC4
C4C41
C4C5
C5C6
C5C51

sup-12

1.332 (2)
1.363 (2)
1.357 (2)
1.394 (2)
1.471 (2)
1.395 (2)
1.508 (2)
1.520 (2)
1.535 (2)
1.362 (2)
1.425 (2)

C34C35
C35C36
C41C42
C41C46
C42C43
C43C44
C44C45
C44O47
C45C46
O47C48
C51N52

1.378 (3)
1.381 (3)
1.376 (3)
1.400 (2)
1.396 (3)
1.387 (3)
1.374 (3)
1.376 (2)
1.375 (3)
1.419 (3)
1.152 (2)

supplementary materials
C6N7
C6C61
C7AN7
C31C32
C31C36
C32C33
C33C34

1.369 (2)
1.482 (2)
1.388 (2)
1.392 (3)
1.394 (3)
1.382 (3)
1.383 (3)

C61C62
C61C66
C62C63
C63C64
C64C65
C65C66

1.391 (2)
1.393 (2)
1.381 (3)
1.383 (3)
1.379 (3)
1.385 (3)

C7AN1N2
C3N2N1
N2C3C3A
N2C3C31
C3AC3C31
C3C3AC7A
C3C3AC4
C7AC3AC4
C3AC4C41
C3AC4C5
C41C4C5
C6C5C51
C6C5C4
C51C5C4
C5C6N7
C5C6C61
N7C6C61
N1C7AN7
N1C7AC3A
N7C7AC3A
C6N7C7A
C32C31C36
C32C31C3
C36C31C3
C33C32C31

102.37 (13)
113.78 (14)
105.82 (15)
121.11 (15)
133.05 (16)
103.90 (15)
134.26 (16)
121.82 (15)
116.23 (14)
108.29 (13)
107.21 (13)
119.77 (16)
125.54 (15)
114.65 (14)
121.14 (16)
123.67 (15)
115.17 (15)
121.81 (15)
114.13 (15)
124.04 (15)
118.52 (14)
117.99 (17)
121.45 (16)
120.55 (16)
120.91 (19)

C32C33C34
C35C34C33
C34C35C36
C35C36C31
C42C41C46
C42C41C4
C46C41C4
C41C42C43
C44C43C42
C45C44O47
C45C44C43
O47C44C43
C44C45C46
C45C46C41
C44O47C48
N52C51C5
C62C61C66
C62C61C6
C66C61C6
C63C62C61
C62C63C64
C65C64C63
C64C65C66
C65C66C61

120.40 (19)
119.19 (19)
120.7 (2)
120.77 (18)
118.41 (16)
122.29 (15)
119.00 (15)
121.21 (17)
118.96 (18)
115.24 (16)
120.51 (17)
124.25 (18)
120.00 (17)
120.91 (17)
117.70 (16)
175.78 (19)
118.73 (16)
119.81 (15)
121.43 (16)
120.50 (17)
120.28 (18)
119.85 (17)
120.08 (17)
120.54 (17)

C7AN1N2C3
N1N2C3C3A
N1N2C3C31
N2C3C3AC7A
C31C3C3AC7A
N2C3C3AC4
C31C3C3AC4
C3C3AC4C41
C7AC3AC4C41
C3C3AC4C5
C7AC3AC4C5
C3AC4C5C6
C41C4C5C6
C3AC4C5C51
C41C4C5C51
C51C5C6N7

0.10 (19)
0.01 (19)
178.48 (15)
0.12 (18)
178.32 (18)
178.34 (17)
3.5 (3)
61.9 (3)
120.10 (18)
177.38 (18)
0.6 (2)
7.2 (2)
118.95 (18)
175.22 (14)
58.64 (18)
172.13 (15)

C32C33C34C35
C33C34C35C36
C34C35C36C31
C32C31C36C35
C3C31C36C35
C3AC4C41C42
C5C4C41C42
C3AC4C41C46
C5C4C41C46
C46C41C42C43
C4C41C42C43
C41C42C43C44
C42C43C44C45
C42C43C44O47
O47C44C45C46
C43C44C45C46

2.3 (4)
0.9 (4)
1.5 (3)
2.4 (3)
178.20 (18)
41.0 (2)
80.28 (19)
145.50 (16)
93.24 (18)
0.0 (3)
173.58 (16)
0.4 (3)
0.2 (3)
178.86 (17)
179.62 (17)
0.5 (3)

sup-13

supplementary materials
C4C5C6N7
C51C5C6C61
C4C5C6C61
N2N1C7AN7
N2N1C7AC3A
C3C3AC7AN1
C4C3AC7AN1
C3C3AC7AN7
C4C3AC7AN7
C5C6N7C7A
C61C6N7C7A
N1C7AN7C6
C3AC7AN7C6
N2C3C31C32
C3AC3C31C32
N2C3C31C36
C3AC3C31C36
C36C31C32C33
C3C31C32C33
C31C32C33C34

10.4 (3)
9.5 (3)
167.99 (15)
178.54 (15)
0.2 (2)
0.2 (2)
178.70 (15)
178.51 (16)
3.0 (3)
6.0 (2)
172.51 (14)
178.70 (16)
0.5 (3)
3.5 (3)
174.44 (18)
175.80 (17)
6.2 (3)
1.0 (3)
179.66 (19)
1.4 (3)

C44C45C46C41
C42C41C46C45
C4C41C46C45
C45C44O47C48
C43C44O47C48
C6C5C51N52
C4C5C51N52
C5C6C61C62
N7C6C61C62
C5C6C61C66
N7C6C61C66
C66C61C62C63
C6C61C62C63
C61C62C63C64
C62C63C64C65
C63C64C65C66
C64C65C66C61
C62C61C66C65
C6C61C66C65

0.9 (3)
0.7 (3)
173.10 (16)
170.21 (17)
8.9 (3)
180 (100)
2(3)
45.5 (2)
132.96 (17)
136.39 (19)
45.1 (2)
1.7 (3)
179.83 (17)
1.2 (3)
0.2 (3)
0.3 (3)
0.2 (3)
1.2 (3)
179.29 (16)

Hydrogen-bond geometry (, )
DHA

DH

HA

DA

DHA

0.88

2.18

3.016 (2)

159

0.88
N7H7N1
Symmetry codes: (i) x, y1, z; (ii) x, y, z+1/2.

2.33

3.065 (2)

142

N2H2N52
ii

3,4-Bis(4-chlorophenyl)-5-cyano-6-phenyl-1H-pyrazolo-[3,4-b]pyridine
Crystal data
C25H14Cl2N4

F000 = 904

Mr = 441.30

Dx = 1.422 Mg m3

Monoclinic, P21/n
a = 6.6222 (5)
b = 11.0791 (10)
c = 28.264 (2)
= 96.248 (5)
V = 2061.3 (3) 3
Z=4

Mo K radiation
= 0.71073
Cell parameters from 4026 reflections
= 2.326.3
= 0.34 mm1
T = 150.0 (1) K
Plate, colourless
0.10 0.10 0.05 mm

Data collection
KappaCCD
diffractometer
Radiation source: fine-focus sealed X-ray tube

sup-14

4026 independent reflections

1975 reflections with I > 2(I)

supplementary materials
Monochromator: graphite

Rint = 0.047

T = 150.0(1) K

max = 26.3

scans and scans with offsets

min = 2.3

Absorption correction: Multi-scan

(SORTAV; Blessing, 1995, 1997)
Tmin = 0.967, Tmax = 0.983

h = 88
k = 1113
l = 3235

15117 measured reflections

Refinement
Refinement on F2

Secondary atom site location: difference Fourier map

Least-squares matrix: full

Hydrogen site location: inferred from neighbouring

sites

R[F2 > 2(F2)] = 0.058

H-atom parameters constrained

w = 1/[2(Fo2) + (0.0409P)2]

wR(F2) = 0.115

where P = (Fo2 + 2Fc2)/3 ?

S = 0.94

(/)max < 0.001

4026 reflections

max = 0.40 e 3

280 parameters

min = 0.28 e 3

Primary atom site location: structure-invariant direct

Extinction correction: none
methods

Special details
Experimental. KappaCCD diffractometer using the following programs. Collect: Data collection software, Hooft, 1998 [Hooft, R.
(1998). Nonius BV, Delft, The Netherlands],is a graphical user interface written by EnrafNonius which encompasses the following
programs. DENZO (Otwinowski and Minor, 1997) and indexing and data collection software package and a scaling package, SCALEPACK both of which programs are produced by the company HKL. Absorption corrections are performed by the SORTAV package,
Blessing, 1995 and Blessing, 1997. High redundancy data were used in the scaling program hence the 'multi-scan' code word was used.
No transmission coefficients are available from the program (only scale factors for each frame). The scale factors in the experimental
table are calculated from the 'size' command in the SHELXL97 input file. Low temperature data is collected using an Oxford Cryosystems cryostream [Cosier, J. & Glazer, AM. (1986). J. Appl. Cryst. 19, 105107].

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (2)
N1
N2
C3
C31
C32
C33
C34
C35
C36
Cl37
C3A

Uiso*/Ueq

0.7963 (4)
0.6437 (4)
0.6680 (4)
0.5247 (4)
0.5898 (5)
0.4557 (5)
0.2515 (4)
0.1811 (5)
0.3176 (5)
0.07847 (12)
0.8393 (4)

0.8827 (2)
0.7991 (2)
0.7354 (3)
0.6366 (3)
0.5243 (3)
0.4323 (3)
0.4518 (3)
0.5597 (3)
0.6516 (3)
0.33802 (8)
0.7796 (3)

0.00787 (8)
0.00473 (8)
0.04475 (10)
0.05163 (9)
0.06994 (10)
0.07651 (10)
0.06418 (10)
0.04473 (10)
0.03844 (10)
0.07379 (3)
0.07528 (10)

0.0323 (7)
0.0327 (7)
0.0273 (8)
0.0281 (8)
0.0323 (8)
0.0331 (8)
0.0325 (8)
0.0343 (9)
0.0338 (9)
0.0480 (3)
0.0265 (8)

sup-15

supplementary materials
C4
C41
C42
C43
C44
C45
C46
Cl47
C5
C51
N52
C6
C61
C62
C63
C64
C65
C66
N7
C7A
H1
H32
H33
H35
H36
H42
H43
H45
H46
H62
H63
H64
H65
H66

0.9369 (4)
0.8737 (4)
1.0024 (5)
0.9463 (5)
0.7595 (5)
0.6269 (5)
0.6835 (4)
0.69224 (14)
1.1026 (4)
1.2083 (4)
1.2858 (4)
1.1679 (4)
1.3380 (4)
1.3350 (5)
1.4895 (6)
1.6519 (5)
1.6572 (5)
1.4992 (4)
1.0783 (3)
0.9174 (4)
0.8132
0.7281
0.5023
0.0430
0.2700
1.1287
1.0328
0.5013
0.5938
1.2273
1.4847
1.7583
1.7656
1.5019

0.7569 (3)
0.6620 (3)
0.5685 (3)
0.4849 (3)
0.4964 (3)
0.5872 (3)
0.6690 (3)
0.39483 (9)
0.8316 (3)
0.8132 (3)
0.7952 (3)
0.9257 (3)
1.0070 (3)
1.0704 (3)
1.1480 (3)
1.1627 (3)
1.1021 (3)
1.0244 (3)
0.9453 (2)
0.8738 (3)
0.9347
0.5112
0.3586
0.5709
0.7244
0.5622
0.4217
0.5932
0.7297
1.0599
1.1911
1.2136
1.1132
0.9838

0.12093 (10)
0.15319 (9)
0.16882 (10)
0.20075 (10)
0.21729 (10)
0.20222 (10)
0.16961 (10)
0.25995 (3)
0.13556 (10)
0.18297 (11)
0.22033 (9)
0.10631 (10)
0.12345 (10)
0.16597 (11)
0.18125 (12)
0.15519 (13)
0.11275 (13)
0.09686 (11)
0.06236 (8)
0.04926 (10)
0.0139
0.0779
0.0890
0.0359
0.0252
0.1575
0.2110
0.2139
0.1584
0.1841
0.2094
0.1663
0.0949
0.0681

0.0268 (8)
0.0266 (8)
0.0321 (8)
0.0379 (9)
0.0333 (8)
0.0358 (9)
0.0323 (8)
0.0548 (3)
0.0284 (8)
0.0307 (8)
0.0406 (8)
0.0293 (8)
0.0290 (8)
0.0406 (9)
0.0499 (10)
0.0478 (10)
0.0463 (10)
0.0356 (9)
0.0285 (7)
0.0283 (8)
0.039*
0.039*
0.040*
0.041*
0.041*
0.039*
0.045*
0.043*
0.039*
0.049*
0.060*
0.057*
0.056*
0.043*

Atomic displacement parameters (2)

N1
N2
C3
C31
C32
C33
C34
C35
C36
Cl37

sup-16

U11
0.0365 (15)
0.0305 (15)
0.0307 (19)
0.0309 (19)
0.0289 (18)
0.041 (2)
0.031 (2)
0.0250 (18)
0.035 (2)
0.0422 (5)

U22
0.0319 (19)
0.038 (2)
0.027 (2)
0.032 (2)
0.035 (2)
0.026 (2)
0.036 (2)
0.038 (3)
0.034 (2)
0.0413 (6)

U33
0.0278 (14)
0.0293 (15)
0.0242 (17)
0.0216 (16)
0.0318 (18)
0.0327 (18)
0.0316 (18)
0.0397 (19)
0.0306 (18)
0.0623 (6)

U12
0.0078 (15)
0.0045 (15)
0.0039 (17)
0.0011 (18)
0.0036 (19)
0.0051 (19)
0.0040 (19)
0.003 (2)
0.0014 (19)
0.0102 (5)

U13
0.0002 (12)
0.0037 (12)
0.0028 (15)
0.0024 (14)
0.0001 (15)
0.0052 (16)
0.0064 (15)
0.0038 (15)
0.0021 (16)
0.0139 (4)

U23
0.0057 (13)
0.0015 (14)
0.0007 (16)
0.0048 (15)
0.0043 (17)
0.0001 (16)
0.0078 (17)
0.0048 (18)
0.0002 (16)
0.0024 (5)

supplementary materials
C3A
C4
C41
C42
C43
C44
C45
C46
Cl47
C5
C51
N52
C6
C61
C62
C63
C64
C65
C66
N7
C7A

0.0265 (18)
0.0253 (18)
0.0270 (18)
0.0294 (18)
0.047 (2)
0.043 (2)
0.0338 (19)
0.0311 (19)
0.0667 (6)
0.0261 (18)
0.0301 (19)
0.0408 (17)
0.0278 (18)
0.0280 (18)
0.046 (2)
0.062 (2)
0.048 (2)
0.031 (2)
0.0320 (19)
0.0288 (15)
0.0272 (18)

0.026 (2)
0.029 (2)
0.031 (2)
0.039 (2)
0.036 (2)
0.030 (2)
0.042 (3)
0.037 (2)
0.0549 (7)
0.033 (2)
0.030 (2)
0.047 (2)
0.031 (2)
0.030 (2)
0.040 (3)
0.047 (3)
0.035 (3)
0.045 (3)
0.035 (2)
0.0336 (18)
0.036 (2)

0.0262 (18)
0.0262 (17)
0.0206 (16)
0.0275 (17)
0.0296 (18)
0.0258 (17)
0.0324 (18)
0.0280 (17)
0.0431 (5)
0.0254 (17)
0.033 (2)
0.0319 (16)
0.0295 (18)
0.0281 (18)
0.0341 (19)
0.038 (2)
0.055 (2)
0.062 (2)
0.0395 (19)
0.0226 (14)
0.0216 (17)

0.0005 (16)
0.0028 (17)
0.0011 (18)
0.0006 (18)
0.0054 (19)
0.0093 (19)
0.0055 (19)
0.0007 (18)
0.0167 (5)
0.0012 (18)
0.0034 (17)
0.0072 (15)
0.0036 (17)
0.0007 (17)
0.007 (2)
0.006 (2)
0.010 (2)
0.005 (2)
0.0020 (19)
0.0019 (15)
0.0075 (18)

0.0017 (15)
0.0060 (14)
0.0027 (14)
0.0015 (15)
0.0025 (17)
0.0013 (16)
0.0090 (16)
0.0016 (15)
0.0067 (5)
0.0009 (14)
0.0068 (16)
0.0040 (14)
0.0033 (15)
0.0025 (15)
0.0018 (17)
0.007 (2)
0.018 (2)
0.0023 (18)
0.0003 (16)
0.0007 (12)
0.0019 (15)

0.0018 (16)
0.0011 (16)
0.0023 (16)
0.0000 (17)
0.0041 (17)
0.0012 (17)
0.0031 (18)
0.0014 (17)
0.0140 (5)
0.0005 (16)
0.0023 (17)
0.0005 (15)
0.0076 (16)
0.0032 (16)
0.0023 (18)
0.0036 (19)
0.000 (2)
0.004 (2)
0.0003 (17)
0.0021 (13)
0.0023 (16)

Geometric parameters (, )
N1C7A
N1N2
N2C3
C3C3A
C3C31
C31C36
C31C32
C32C33
C33C34
C34C35
C34Cl37
C35C36
C3AC4
C3AC7A
C4C5
C4C41
C41C42
C41C46

1.348 (3)
1.367 (3)
1.328 (3)
1.435 (4)
1.475 (4)
1.392 (4)
1.398 (4)
1.377 (4)
1.377 (4)
1.376 (4)
1.744 (3)
1.385 (4)
1.401 (4)
1.407 (4)
1.400 (4)
1.482 (4)
1.383 (4)
1.391 (4)

C42C43
C43C44
C44C45
C44Cl47
C45C46
C5C6
C5C51
C51N52
C6N7
C6C61
C61C66
C61C62
C62C63
C63C64
C64C65
C65C66
N7C7A

1.372 (4)
1.375 (4)
1.372 (4)
1.742 (3)
1.373 (4)
1.427 (4)
1.457 (4)
1.140 (3)
1.335 (3)
1.482 (4)
1.384 (4)
1.394 (4)
1.370 (4)
1.378 (4)
1.378 (4)
1.392 (4)
1.347 (4)

C7AN1N2
C3N2N1
N2C3C3A
N2C3C31
C3AC3C31
C36C31C32
C36C31C3

111.9 (2)
106.5 (2)
110.2 (3)
119.1 (3)
130.7 (3)
117.4 (3)
120.4 (3)

C42C43C44
C45C44C43
C45C44Cl47
C43C44Cl47
C44C45C46
C45C46C41
C4C5C6

118.6 (3)
122.1 (3)
119.0 (2)
118.9 (3)
118.7 (3)
120.7 (3)
122.5 (3)

sup-17

supplementary materials
C32C31C3
C33C32C31
C34C33C32
C35C34C33
C35C34Cl37
C33C34Cl37
C34C35C36
C35C36C31
C4C3AC7A
C4C3AC3
C7AC3AC3
C5C4C3A
C5C4C41
C3AC4C41
C42C41C46
C42C41C4
C46C41C4
C43C42C41

122.1 (3)
122.0 (3)
118.7 (3)
121.2 (3)
119.4 (2)
119.5 (3)
119.5 (3)
121.0 (3)
117.1 (3)
138.3 (3)
104.5 (2)
115.7 (3)
120.2 (3)
124.1 (3)
118.9 (3)
121.5 (3)
119.5 (3)
121.0 (3)

C4C5C51
C6C5C51
N52C51C5
N7C6C5
N7C6C61
C5C6C61
C66C61C62
C66C61C6
C62C61C6
C63C62C61
C62C63C64
C63C64C65
C64C65C66
C61C66C65
C6N7C7A
N7C7AN1
N7C7AC3A
N1C7AC3A

118.1 (3)
119.3 (3)
177.3 (3)
121.7 (3)
116.8 (3)
121.5 (3)
118.9 (3)
120.7 (3)
120.4 (3)
120.5 (3)
120.3 (3)
120.2 (3)
119.5 (3)
120.5 (3)
114.7 (3)
125.0 (3)
128.1 (3)
106.9 (3)

C7AN1N2C3
N1N2C3C3A
N1N2C3C31
N2C3C31C36
C3AC3C31C36
N2C3C31C32
C3AC3C31C32
C36C31C32C33
C3C31C32C33
C31C32C33C34
C32C33C34C35
C32C33C34Cl37
C33C34C35C36
Cl37C34C35C36
C34C35C36C31
C32C31C36C35
C3C31C36C35
N2C3C3AC4
C31C3C3AC4
N2C3C3AC7A
C31C3C3AC7A
C7AC3AC4C5
C3C3AC4C5
C7AC3AC4C41
C3C3AC4C41
C5C4C41C42
C3AC4C41C42
C5C4C41C46
C3AC4C41C46
C46C41C42C43
C4C41C42C43

0.2 (3)
0.9 (3)
179.6 (3)
41.8 (4)
137.5 (3)
136.2 (3)
44.5 (5)
2.3 (4)
179.7 (3)
0.6 (4)
1.3 (4)
178.2 (2)
1.5 (5)
178.0 (2)
0.2 (5)
2.0 (4)
179.9 (3)
176.8 (3)
2.6 (6)
1.3 (3)
179.4 (3)
0.1 (4)
177.8 (3)
179.5 (3)
1.6 (6)
61.6 (4)
119.0 (3)
116.0 (3)
63.4 (4)
1.3 (4)
176.4 (3)

C44C45C46C41
C42C41C46C45
C4C41C46C45
C3AC4C5C6
C41C4C5C6
C3AC4C5C51
C41C4C5C51
C4C5C51N52
C6C5C51N52
C4C5C6N7
C51C5C6N7
C4C5C6C61
C51C5C6C61
N7C6C61C66
C5C6C61C66
N7C6C61C62
C5C6C61C62
C66C61C62C63
C6C61C62C63
C61C62C63C64
C62C63C64C65
C63C64C65C66
C62C61C66C65
C6C61C66C65
C64C65C66C61
C5C6N7C7A
C61C6N7C7A
C6N7C7AN1
C6N7C7AC3A
N2N1C7AN7
N2N1C7AC3A

1.8 (4)
2.5 (4)
175.2 (3)
0.5 (4)
178.9 (3)
179.2 (3)
0.3 (4)
0(7)
179 (100)
2.3 (4)
179.0 (3)
177.2 (3)
1.4 (4)
52.6 (4)
127.9 (3)
125.4 (3)
54.2 (4)
0.3 (5)
178.3 (3)
1.3 (5)
2.0 (5)
1.2 (5)
1.1 (5)
179.1 (3)
0.4 (5)
3.2 (4)
176.4 (3)
175.5 (3)
2.7 (4)
179.2 (3)
0.6 (3)

sup-18

supplementary materials
C41C42C43C44
C42C43C44C45
C42C43C44Cl47
C43C44C45C46
Cl47C44C45C46

0.5 (4)
1.2 (5)
177.0 (2)
0.1 (5)
178.1 (2)

C4C3AC7AN7
C3C3AC7AN7
C4C3AC7AN1
C3C3AC7AN1

1.1 (5)
179.6 (3)
177.4 (2)
1.1 (3)

Hydrogen-bond geometry (, )
DHA

DH

HA

DA

DHA

N1H1N7i
Symmetry codes: (i) x+2, y+2, z.

0.88

2.07

2.935 (3)

167

sup-19