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Both 6-(1
H-indol-3-yl)-3-methyl-4-(4-methylphenyl)-1-phenyl-1
H-pyrazolo[3,4-
b]pyridine-5-carbonitrile and 6-(1
H-indol-3-yl)-3-methyl-4-(4-methoxyphenyl)-1-phenyl-1
H-pyrazolo[3,4-
b]pyridine-5-carbonitrile crystallize from dimethylformamide solutions as stoichiometric 1:1 solvates,
viz. C
29H
21N
5·C
3H
7NO, (I), and C
29H
21N
5O·C
3H
7NO, (II), respectively; however, 6-(1
H-indol-3-yl)-3-methyl-1-phenyl-4-(3,4,5-trimethoxyphenyl)-1
H-pyrazolo[3,4-
b]pyridine-5-carbonitrile, C
31H
25N
5O
3, (III), crystallizes in the unsolvated form. The heterocyclic components of (I) are linked by C—H
π(arene) hydrogen bonds to form cyclic centrosymmetric dimers, from which the solvent molecules are pendent, linked by N—H
O hydrogen bonds. In (II), the heterocyclic components are linked by a combination of C—H
N and C—H
π(arene) hydrogen bonds into chains containing two types of centrosymmetric ring, and the pendent solvent molecules are linked to these chains by N—H
O hydrogen bonds. Molecules of (III) are linked into simple
C(12) chains by an N—H
O hydrogen bond, and these chains are weakly linked into pairs by an aromatic π–π stacking interaction.
Supporting information
CCDC references: 649085; 649086; 649087
Equimolar mixtures (0.5 mmol of each component) of
5-amino-3-methyl-1-phenylpyrazole, 3-(2-cyanoacetyl)indole and the appropriate
aldehyde [4-methylbenzaldehyde for (I), 4-methoxybenzaldehyde for (II) and
3,4,5-trimethoxybenzaldehyde for (III)] were subjected to microwave
irradiation in the absence of solvent (maximum power 300 W during 9 min at a
controlled temperature of 473 K) using a focused microwave reactor (CEM
Discover). The resulting reaction mixtures were then extracted with hot
ethanol/dimethylformamide mixtures (2:1 v/v): the solid products
were collected by filtration and washed successively with ethanol and diethyl
ether to yield crystals of compounds (I)–(III) suitable for single-crystal
X-ray diffraction. Compound (I), yield 89%, m.p. 547 K; MS (70 eV)
m/z (%) = 439(100, M+), 424 (37), 397 (6), 77 (40),
51 (30). Compound (II), yield 85%, m.p. 543 K; MS (70 eV) m/z (%)
= 455 (100, M+), 424 (9), 409 (6), 77 (8). Compound (III), yield 88%,
m.p. 548; MS (70 eV) m/z (%) = 515 (100, M+), 484 (23),
414 (8), 258 (10), 77 (31), 51 (13).
Crystals of compounds (I) and (III) are triclinic; for each compound space group
P1 was selected, and confirmed by the structure analysis. For
compound (II), the systematic absences permitted C2/c and
Cc as possible space groups; C2/c was selected, and
confirmed by the structure analysis. All H atoms were located in difference
maps, and then treated as riding atoms with C—H distances of 0.95 Å
(aromatic and formyl) or 0.98 Å (methyl) and N—H of 0.88 Å, and with
Uiso(H) = kUeq(carrier), where k = 1.5 for the methyl
groups and k = 1.2 for all other H atoms.
For all compounds, data collection: COLLECT (Hooft, 1999); cell refinement: DIRAX/LSQ (Duisenberg et al., 2000); data reduction: EVALCCD (Duisenberg et al., 2003); program(s) used to solve structure: SIR2004 (Burla et al., 2005); program(s) used to refine structure: OSCAIL (McArdle, 2003) and SHELXL97 (Sheldrick, 1997); molecular graphics: PLATON (Spek, 2003); software used to prepare material for publication: SHELXL97 and PRPKAPPA (Ferguson, 1999).
(I) 6-(1
H-indol-3-yl)-3-methyl-4-(4-methylphenyl)-1-phenyl-1
H-
pyrazolo[3,4-
b]pyridine-5-carbonitrile
top
Crystal data top
C29H21N5·C3H7NO | Z = 2 |
Mr = 512.60 | F(000) = 540 |
Triclinic, P1 | Dx = 1.297 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 9.8060 (3) Å | Cell parameters from 5996 reflections |
b = 10.1820 (3) Å | θ = 3.0–27.5° |
c = 13.818 (2) Å | µ = 0.08 mm−1 |
α = 97.035 (6)° | T = 120 K |
β = 104.455 (6)° | Block, colourless |
γ = 96.171 (3)° | 0.40 × 0.18 × 0.18 mm |
V = 1312.2 (2) Å3 | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 5996 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 3816 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.048 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.0° |
ϕ & ω scans | h = −12→12 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→13 |
Tmin = 0.961, Tmax = 0.985 | l = −17→17 |
31081 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.050 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0617P)2 + 0.7281P] where P = (Fo2 + 2Fc2)/3 |
5996 reflections | (Δ/σ)max < 0.001 |
356 parameters | Δρmax = 0.37 e Å−3 |
0 restraints | Δρmin = −0.31 e Å−3 |
Crystal data top
C29H21N5·C3H7NO | γ = 96.171 (3)° |
Mr = 512.60 | V = 1312.2 (2) Å3 |
Triclinic, P1 | Z = 2 |
a = 9.8060 (3) Å | Mo Kα radiation |
b = 10.1820 (3) Å | µ = 0.08 mm−1 |
c = 13.818 (2) Å | T = 120 K |
α = 97.035 (6)° | 0.40 × 0.18 × 0.18 mm |
β = 104.455 (6)° | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 5996 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3816 reflections with I > 2σ(I) |
Tmin = 0.961, Tmax = 0.985 | Rint = 0.048 |
31081 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.050 | 0 restraints |
wR(F2) = 0.146 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.37 e Å−3 |
5996 reflections | Δρmin = −0.31 e Å−3 |
356 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.17256 (17) | 0.43480 (15) | 0.53720 (12) | 0.0223 (4) | |
C11 | 0.0798 (2) | 0.32981 (19) | 0.46645 (15) | 0.0231 (4) | |
C12 | −0.0323 (2) | 0.2628 (2) | 0.49438 (16) | 0.0269 (5) | |
C13 | −0.1234 (2) | 0.1595 (2) | 0.42691 (17) | 0.0327 (5) | |
C14 | −0.1064 (2) | 0.1244 (2) | 0.33136 (17) | 0.0324 (5) | |
C15 | 0.0056 (2) | 0.1910 (2) | 0.30436 (17) | 0.0320 (5) | |
C16 | 0.1003 (2) | 0.2927 (2) | 0.37157 (15) | 0.0275 (5) | |
N2 | 0.16228 (18) | 0.45428 (16) | 0.63587 (12) | 0.0255 (4) | |
C3 | 0.2590 (2) | 0.55566 (19) | 0.68598 (15) | 0.0238 (4) | |
C31 | 0.2692 (2) | 0.6014 (2) | 0.79472 (15) | 0.0309 (5) | |
C3A | 0.3375 (2) | 0.60717 (19) | 0.62060 (14) | 0.0218 (4) | |
C4 | 0.4431 (2) | 0.71493 (18) | 0.62641 (14) | 0.0215 (4) | |
C41 | 0.5144 (2) | 0.80261 (19) | 0.72421 (14) | 0.0218 (4) | |
C42 | 0.5853 (2) | 0.7467 (2) | 0.80643 (15) | 0.0279 (5) | |
C43 | 0.6468 (2) | 0.8245 (2) | 0.89987 (15) | 0.0287 (5) | |
C44 | 0.6389 (2) | 0.9605 (2) | 0.91438 (15) | 0.0256 (4) | |
C441 | 0.7015 (2) | 1.0440 (2) | 1.01756 (16) | 0.0350 (5) | |
C45 | 0.5709 (2) | 1.0160 (2) | 0.83178 (15) | 0.0268 (5) | |
C46 | 0.5096 (2) | 0.93929 (19) | 0.73794 (15) | 0.0248 (4) | |
C5 | 0.47434 (19) | 0.73448 (18) | 0.53544 (14) | 0.0213 (4) | |
C51 | 0.5754 (2) | 0.8462 (2) | 0.53358 (15) | 0.0256 (4) | |
N51 | 0.65463 (19) | 0.93516 (18) | 0.52840 (14) | 0.0342 (4) | |
C6 | 0.40680 (19) | 0.64614 (18) | 0.44291 (14) | 0.0206 (4) | |
C61 | 0.4389 (2) | 0.65856 (18) | 0.34648 (14) | 0.0210 (4) | |
C62 | 0.5649 (2) | 0.71023 (19) | 0.32929 (15) | 0.0238 (4) | |
N63 | 0.55728 (17) | 0.68867 (16) | 0.22899 (12) | 0.0252 (4) | |
C63A | 0.4247 (2) | 0.62111 (18) | 0.17701 (14) | 0.0224 (4) | |
C64 | 0.3699 (2) | 0.5764 (2) | 0.07383 (15) | 0.0280 (5) | |
C65 | 0.2335 (2) | 0.5086 (2) | 0.04160 (16) | 0.0313 (5) | |
C66 | 0.1523 (2) | 0.4892 (2) | 0.11050 (15) | 0.0289 (5) | |
C67 | 0.2061 (2) | 0.53492 (19) | 0.21261 (15) | 0.0247 (4) | |
C67A | 0.3468 (2) | 0.60076 (18) | 0.24838 (14) | 0.0213 (4) | |
N7 | 0.30754 (16) | 0.54313 (15) | 0.43858 (12) | 0.0215 (4) | |
C7A | 0.2762 (2) | 0.52825 (18) | 0.52556 (14) | 0.0216 (4) | |
N20 | 1.02010 (18) | 0.83307 (17) | 0.20145 (13) | 0.0286 (4) | |
C20 | 0.8953 (2) | 0.7928 (2) | 0.21673 (16) | 0.0273 (5) | |
O20 | 0.78473 (15) | 0.74965 (15) | 0.14953 (11) | 0.0329 (4) | |
C21 | 1.1434 (2) | 0.8874 (2) | 0.28574 (18) | 0.0365 (5) | |
C22 | 1.0394 (2) | 0.8270 (2) | 0.10081 (17) | 0.0382 (6) | |
H12 | −0.0462 | 0.2878 | 0.5594 | 0.032* | |
H13 | −0.1984 | 0.1122 | 0.4466 | 0.039* | |
H14 | −0.1710 | 0.0553 | 0.2846 | 0.039* | |
H15 | 0.0179 | 0.1667 | 0.2388 | 0.038* | |
H16 | 0.1783 | 0.3365 | 0.3529 | 0.033* | |
H31A | 0.1842 | 0.5612 | 0.8114 | 0.046* | |
H31B | 0.2760 | 0.6991 | 0.8069 | 0.046* | |
H31C | 0.3539 | 0.5740 | 0.8372 | 0.046* | |
H42 | 0.5914 | 0.6537 | 0.7981 | 0.033* | |
H43 | 0.6949 | 0.7843 | 0.9547 | 0.034* | |
H44A | 0.7002 | 1.1389 | 1.0118 | 0.053* | |
H44B | 0.7998 | 1.0284 | 1.0442 | 0.053* | |
H44C | 0.6450 | 1.0189 | 1.0635 | 0.053* | |
H45 | 0.5663 | 1.1093 | 0.8399 | 0.032* | |
H46 | 0.4640 | 0.9802 | 0.6828 | 0.030* | |
H62 | 0.6460 | 0.7548 | 0.3805 | 0.029* | |
H63 | 0.6259 | 0.7138 | 0.2016 | 0.030* | |
H64 | 0.4246 | 0.5921 | 0.0274 | 0.034* | |
H65 | 0.1938 | 0.4744 | −0.0281 | 0.038* | |
H66 | 0.0577 | 0.4434 | 0.0861 | 0.035* | |
H67 | 0.1491 | 0.5222 | 0.2580 | 0.030* | |
H20 | 0.8904 | 0.7975 | 0.2848 | 0.033* | |
H21A | 1.1146 | 0.8956 | 0.3490 | 0.055* | |
H21B | 1.1829 | 0.9757 | 0.2758 | 0.055* | |
H21C | 1.2157 | 0.8274 | 0.2892 | 0.055* | |
H22A | 0.9502 | 0.7867 | 0.0510 | 0.057* | |
H22B | 1.1143 | 0.7725 | 0.0946 | 0.057* | |
H22C | 1.0670 | 0.9175 | 0.0885 | 0.057* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0242 (9) | 0.0240 (8) | 0.0187 (8) | 0.0008 (7) | 0.0062 (7) | 0.0050 (7) |
C11 | 0.0226 (10) | 0.0206 (10) | 0.0249 (10) | 0.0038 (8) | 0.0022 (8) | 0.0065 (8) |
C12 | 0.0241 (10) | 0.0268 (11) | 0.0297 (11) | 0.0029 (8) | 0.0063 (9) | 0.0063 (9) |
C13 | 0.0235 (11) | 0.0283 (11) | 0.0455 (14) | 0.0002 (9) | 0.0069 (10) | 0.0102 (10) |
C14 | 0.0294 (11) | 0.0239 (11) | 0.0376 (13) | 0.0006 (9) | 0.0014 (10) | −0.0009 (9) |
C15 | 0.0354 (12) | 0.0261 (11) | 0.0314 (12) | 0.0033 (9) | 0.0064 (10) | −0.0006 (9) |
C16 | 0.0288 (11) | 0.0240 (10) | 0.0294 (11) | 0.0015 (9) | 0.0081 (9) | 0.0036 (9) |
N2 | 0.0314 (9) | 0.0278 (9) | 0.0188 (9) | 0.0039 (7) | 0.0085 (7) | 0.0052 (7) |
C3 | 0.0286 (11) | 0.0224 (10) | 0.0212 (10) | 0.0052 (8) | 0.0060 (8) | 0.0061 (8) |
C31 | 0.0379 (12) | 0.0332 (12) | 0.0217 (11) | 0.0027 (10) | 0.0094 (9) | 0.0044 (9) |
C3A | 0.0255 (10) | 0.0215 (10) | 0.0190 (10) | 0.0052 (8) | 0.0058 (8) | 0.0047 (8) |
C4 | 0.0223 (10) | 0.0212 (10) | 0.0207 (10) | 0.0063 (8) | 0.0031 (8) | 0.0045 (8) |
C41 | 0.0223 (10) | 0.0222 (10) | 0.0202 (10) | 0.0015 (8) | 0.0054 (8) | 0.0024 (8) |
C42 | 0.0345 (12) | 0.0222 (10) | 0.0247 (11) | 0.0050 (9) | 0.0040 (9) | 0.0023 (8) |
C43 | 0.0293 (11) | 0.0308 (11) | 0.0229 (11) | 0.0024 (9) | 0.0021 (9) | 0.0042 (9) |
C44 | 0.0252 (10) | 0.0278 (11) | 0.0226 (10) | −0.0007 (8) | 0.0083 (8) | −0.0006 (8) |
C441 | 0.0382 (13) | 0.0359 (12) | 0.0264 (12) | −0.0025 (10) | 0.0084 (10) | −0.0058 (9) |
C45 | 0.0308 (11) | 0.0198 (10) | 0.0297 (11) | 0.0014 (8) | 0.0105 (9) | −0.0001 (8) |
C46 | 0.0252 (10) | 0.0242 (10) | 0.0250 (11) | 0.0034 (8) | 0.0060 (8) | 0.0060 (8) |
C5 | 0.0201 (10) | 0.0214 (10) | 0.0218 (10) | 0.0023 (8) | 0.0039 (8) | 0.0048 (8) |
C51 | 0.0248 (11) | 0.0300 (11) | 0.0208 (10) | 0.0028 (9) | 0.0044 (8) | 0.0035 (8) |
N51 | 0.0334 (10) | 0.0355 (11) | 0.0292 (10) | −0.0080 (9) | 0.0067 (8) | 0.0019 (8) |
C6 | 0.0182 (9) | 0.0217 (10) | 0.0221 (10) | 0.0034 (8) | 0.0044 (8) | 0.0052 (8) |
C61 | 0.0244 (10) | 0.0200 (9) | 0.0196 (10) | 0.0048 (8) | 0.0061 (8) | 0.0043 (8) |
C62 | 0.0265 (10) | 0.0234 (10) | 0.0212 (10) | 0.0039 (8) | 0.0055 (8) | 0.0041 (8) |
N63 | 0.0261 (9) | 0.0277 (9) | 0.0252 (9) | 0.0033 (7) | 0.0112 (7) | 0.0082 (7) |
C63A | 0.0259 (10) | 0.0203 (10) | 0.0220 (10) | 0.0051 (8) | 0.0067 (8) | 0.0053 (8) |
C64 | 0.0367 (12) | 0.0290 (11) | 0.0216 (11) | 0.0067 (9) | 0.0122 (9) | 0.0060 (9) |
C65 | 0.0411 (13) | 0.0330 (12) | 0.0187 (10) | 0.0060 (10) | 0.0057 (9) | 0.0035 (9) |
C66 | 0.0275 (11) | 0.0314 (11) | 0.0245 (11) | 0.0002 (9) | 0.0028 (9) | 0.0037 (9) |
C67 | 0.0258 (10) | 0.0257 (10) | 0.0220 (10) | 0.0028 (8) | 0.0057 (8) | 0.0037 (8) |
C67A | 0.0277 (10) | 0.0182 (9) | 0.0196 (10) | 0.0046 (8) | 0.0083 (8) | 0.0043 (8) |
N7 | 0.0219 (8) | 0.0232 (8) | 0.0194 (8) | 0.0029 (7) | 0.0055 (7) | 0.0037 (7) |
C7A | 0.0216 (10) | 0.0209 (10) | 0.0215 (10) | 0.0037 (8) | 0.0038 (8) | 0.0040 (8) |
N20 | 0.0248 (9) | 0.0300 (9) | 0.0288 (10) | −0.0012 (7) | 0.0073 (7) | 0.0001 (8) |
C20 | 0.0303 (11) | 0.0267 (11) | 0.0245 (11) | 0.0006 (9) | 0.0087 (9) | 0.0032 (9) |
O20 | 0.0256 (8) | 0.0430 (9) | 0.0276 (8) | −0.0043 (7) | 0.0071 (6) | 0.0037 (7) |
C21 | 0.0281 (12) | 0.0351 (12) | 0.0403 (14) | 0.0009 (10) | 0.0014 (10) | 0.0021 (10) |
C22 | 0.0359 (13) | 0.0468 (14) | 0.0330 (13) | −0.0022 (11) | 0.0164 (10) | 0.0021 (11) |
Geometric parameters (Å, º) top
N1—C7A | 1.369 (2) | C45—H45 | 0.95 |
N1—N2 | 1.384 (2) | C46—H46 | 0.95 |
N1—C11 | 1.420 (2) | C5—C6 | 1.432 (3) |
C11—C16 | 1.389 (3) | C5—C51 | 1.433 (3) |
C11—C12 | 1.392 (3) | C51—N51 | 1.150 (3) |
C12—C13 | 1.384 (3) | C6—N7 | 1.337 (2) |
C12—H12 | 0.95 | C6—C61 | 1.460 (3) |
C13—C14 | 1.380 (3) | C61—C62 | 1.378 (3) |
C13—H13 | 0.95 | C61—C67A | 1.442 (3) |
C14—C15 | 1.382 (3) | C62—N63 | 1.358 (2) |
C14—H14 | 0.95 | C62—H62 | 0.95 |
C15—C16 | 1.387 (3) | N63—C63A | 1.378 (2) |
C15—H15 | 0.95 | N63—H63 | 0.88 |
C16—H16 | 0.95 | C63A—C64 | 1.391 (3) |
N2—C3 | 1.316 (3) | C63A—C67A | 1.411 (3) |
C3—C3A | 1.435 (3) | C64—C65 | 1.376 (3) |
C3—C31 | 1.493 (3) | C64—H64 | 0.95 |
C31—H31A | 0.98 | C65—C66 | 1.404 (3) |
C31—H31B | 0.98 | C65—H65 | 0.95 |
C31—H31C | 0.98 | C66—C67 | 1.379 (3) |
C3A—C7A | 1.405 (3) | C66—H66 | 0.95 |
C3A—C4 | 1.406 (3) | C67—C67A | 1.406 (3) |
C4—C5 | 1.398 (3) | C67—H67 | 0.95 |
C4—C41 | 1.487 (3) | N7—C7A | 1.335 (2) |
C41—C46 | 1.389 (3) | N20—C20 | 1.324 (3) |
C41—C42 | 1.396 (3) | N20—C22 | 1.445 (3) |
C42—C43 | 1.384 (3) | N20—C21 | 1.456 (3) |
C42—H42 | 0.95 | C20—O20 | 1.235 (2) |
C43—C44 | 1.388 (3) | C20—H20 | 0.95 |
C43—H43 | 0.95 | C21—H21A | 0.98 |
C44—C45 | 1.388 (3) | C21—H21B | 0.98 |
C44—C441 | 1.512 (3) | C21—H21C | 0.98 |
C441—H44A | 0.98 | C22—H22A | 0.98 |
C441—H44B | 0.98 | C22—H22B | 0.98 |
C441—H44C | 0.98 | C22—H22C | 0.98 |
C45—C46 | 1.384 (3) | | |
| | | |
C7A—N1—N2 | 110.04 (15) | C45—C46—H46 | 119.9 |
C7A—N1—C11 | 130.79 (16) | C41—C46—H46 | 119.9 |
N2—N1—C11 | 119.17 (15) | C4—C5—C6 | 121.70 (17) |
C16—C11—C12 | 120.13 (18) | C4—C5—C51 | 119.69 (17) |
C16—C11—N1 | 121.24 (17) | C6—C5—C51 | 118.61 (17) |
C12—C11—N1 | 118.63 (18) | N51—C51—C5 | 177.6 (2) |
C13—C12—C11 | 119.6 (2) | N7—C6—C5 | 121.65 (17) |
C13—C12—H12 | 120.2 | N7—C6—C61 | 114.18 (16) |
C11—C12—H12 | 120.2 | C5—C6—C61 | 124.17 (17) |
C14—C13—C12 | 120.7 (2) | C62—C61—C67A | 105.76 (17) |
C14—C13—H13 | 119.6 | C62—C61—C6 | 128.65 (18) |
C12—C13—H13 | 119.6 | C67A—C61—C6 | 125.12 (17) |
C13—C14—C15 | 119.3 (2) | N63—C62—C61 | 110.67 (17) |
C13—C14—H14 | 120.3 | N63—C62—H62 | 124.7 |
C15—C14—H14 | 120.3 | C61—C62—H62 | 124.7 |
C14—C15—C16 | 121.0 (2) | C62—N63—C63A | 108.97 (16) |
C14—C15—H15 | 119.5 | C62—N63—H63 | 125.5 |
C16—C15—H15 | 119.5 | C63A—N63—H63 | 125.5 |
C15—C16—C11 | 119.19 (19) | N63—C63A—C64 | 129.25 (18) |
C15—C16—H16 | 120.4 | N63—C63A—C67A | 107.65 (16) |
C11—C16—H16 | 120.4 | C64—C63A—C67A | 123.10 (18) |
C3—N2—N1 | 107.57 (16) | C65—C64—C63A | 117.41 (19) |
N2—C3—C3A | 110.37 (17) | C65—C64—H64 | 121.3 |
N2—C3—C31 | 119.09 (18) | C63A—C64—H64 | 121.3 |
C3A—C3—C31 | 130.51 (18) | C64—C65—C66 | 120.81 (19) |
C3—C31—H31A | 109.5 | C64—C65—H65 | 119.6 |
C3—C31—H31B | 109.5 | C66—C65—H65 | 119.6 |
H31A—C31—H31B | 109.5 | C67—C66—C65 | 121.69 (19) |
C3—C31—H31C | 109.5 | C67—C66—H66 | 119.2 |
H31A—C31—H31C | 109.5 | C65—C66—H66 | 119.2 |
H31B—C31—H31C | 109.5 | C66—C67—C67A | 118.87 (19) |
C7A—C3A—C4 | 117.53 (17) | C66—C67—H67 | 120.6 |
C7A—C3A—C3 | 104.80 (17) | C67A—C67—H67 | 120.6 |
C4—C3A—C3 | 137.41 (18) | C67—C67A—C63A | 118.07 (17) |
C5—C4—C3A | 116.03 (17) | C67—C67A—C61 | 134.97 (18) |
C5—C4—C41 | 122.95 (17) | C63A—C67A—C61 | 106.96 (17) |
C3A—C4—C41 | 121.02 (17) | C7A—N7—C6 | 115.80 (16) |
C46—C41—C42 | 118.23 (18) | N7—C7A—N1 | 125.53 (17) |
C46—C41—C4 | 122.10 (17) | N7—C7A—C3A | 127.24 (17) |
C42—C41—C4 | 119.64 (17) | N1—C7A—C3A | 107.18 (16) |
C43—C42—C41 | 121.08 (19) | C20—N20—C22 | 121.64 (18) |
C43—C42—H42 | 119.5 | C20—N20—C21 | 121.19 (18) |
C41—C42—H42 | 119.5 | C22—N20—C21 | 117.17 (18) |
C42—C43—C44 | 120.76 (19) | O20—C20—N20 | 125.2 (2) |
C42—C43—H43 | 119.6 | O20—C20—H20 | 117.4 |
C44—C43—H43 | 119.6 | N20—C20—H20 | 117.4 |
C45—C44—C43 | 117.86 (18) | N20—C21—H21A | 109.5 |
C45—C44—C441 | 121.62 (18) | N20—C21—H21B | 109.5 |
C43—C44—C441 | 120.52 (19) | H21A—C21—H21B | 109.5 |
C44—C441—H44A | 109.5 | N20—C21—H21C | 109.5 |
C44—C441—H44B | 109.5 | H21A—C21—H21C | 109.5 |
H44A—C441—H44B | 109.5 | H21B—C21—H21C | 109.5 |
C44—C441—H44C | 109.5 | N20—C22—H22A | 109.5 |
H44A—C441—H44C | 109.5 | N20—C22—H22B | 109.5 |
H44B—C441—H44C | 109.5 | H22A—C22—H22B | 109.5 |
C46—C45—C44 | 121.87 (18) | N20—C22—H22C | 109.5 |
C46—C45—H45 | 119.1 | H22A—C22—H22C | 109.5 |
C44—C45—H45 | 119.1 | H22B—C22—H22C | 109.5 |
C45—C46—C41 | 120.17 (18) | | |
| | | |
C7A—N1—C11—C16 | 11.4 (3) | C4—C5—C6—N7 | 2.0 (3) |
N2—N1—C11—C16 | −169.71 (17) | C51—C5—C6—N7 | −177.35 (17) |
C7A—N1—C11—C12 | −169.39 (18) | C4—C5—C6—C61 | −177.64 (17) |
N2—N1—C11—C12 | 9.5 (3) | C51—C5—C6—C61 | 3.0 (3) |
C16—C11—C12—C13 | −0.3 (3) | N7—C6—C61—C62 | −150.40 (19) |
N1—C11—C12—C13 | −179.51 (18) | C5—C6—C61—C62 | 29.3 (3) |
C11—C12—C13—C14 | −1.6 (3) | N7—C6—C61—C67A | 20.5 (3) |
C12—C13—C14—C15 | 2.0 (3) | C5—C6—C61—C67A | −159.76 (18) |
C13—C14—C15—C16 | −0.4 (3) | C67A—C61—C62—N63 | 0.0 (2) |
C14—C15—C16—C11 | −1.5 (3) | C6—C61—C62—N63 | 172.28 (18) |
C12—C11—C16—C15 | 1.8 (3) | C61—C62—N63—C63A | −0.2 (2) |
N1—C11—C16—C15 | −178.97 (18) | C62—N63—C63A—C64 | −179.02 (19) |
C7A—N1—N2—C3 | −1.3 (2) | C62—N63—C63A—C67A | 0.3 (2) |
C11—N1—N2—C3 | 179.60 (16) | N63—C63A—C64—C65 | 178.79 (19) |
N1—N2—C3—C3A | 0.0 (2) | C67A—C63A—C64—C65 | −0.5 (3) |
N1—N2—C3—C31 | 178.33 (16) | C63A—C64—C65—C66 | 1.8 (3) |
N2—C3—C3A—C7A | 1.2 (2) | C64—C65—C66—C67 | −1.1 (3) |
C31—C3—C3A—C7A | −176.9 (2) | C65—C66—C67—C67A | −1.0 (3) |
N2—C3—C3A—C4 | 174.9 (2) | C66—C67—C67A—C63A | 2.2 (3) |
C31—C3—C3A—C4 | −3.2 (4) | C66—C67—C67A—C61 | −178.6 (2) |
C7A—C3A—C4—C5 | 1.4 (3) | N63—C63A—C67A—C67 | 179.03 (16) |
C3—C3A—C4—C5 | −171.7 (2) | C64—C63A—C67A—C67 | −1.6 (3) |
C7A—C3A—C4—C41 | −179.38 (17) | N63—C63A—C67A—C61 | −0.4 (2) |
C3—C3A—C4—C41 | 7.5 (3) | C64—C63A—C67A—C61 | 179.05 (17) |
C5—C4—C41—C46 | 58.5 (3) | C62—C61—C67A—C67 | −179.0 (2) |
C3A—C4—C41—C46 | −120.6 (2) | C6—C61—C67A—C67 | 8.3 (3) |
C5—C4—C41—C42 | −123.4 (2) | C62—C61—C67A—C63A | 0.2 (2) |
C3A—C4—C41—C42 | 57.4 (3) | C6—C61—C67A—C63A | −172.42 (17) |
C46—C41—C42—C43 | 1.3 (3) | C5—C6—N7—C7A | −0.1 (3) |
C4—C41—C42—C43 | −176.82 (19) | C61—C6—N7—C7A | 179.59 (16) |
C41—C42—C43—C44 | 0.3 (3) | C6—N7—C7A—N1 | 175.99 (17) |
C42—C43—C44—C45 | −1.6 (3) | C6—N7—C7A—C3A | −1.1 (3) |
C42—C43—C44—C441 | 177.70 (19) | N2—N1—C7A—N7 | −175.59 (17) |
C43—C44—C45—C46 | 1.4 (3) | C11—N1—C7A—N7 | 3.4 (3) |
C441—C44—C45—C46 | −177.96 (19) | N2—N1—C7A—C3A | 2.0 (2) |
C44—C45—C46—C41 | 0.2 (3) | C11—N1—C7A—C3A | −179.00 (18) |
C42—C41—C46—C45 | −1.5 (3) | C4—C3A—C7A—N7 | 0.5 (3) |
C4—C41—C46—C45 | 176.50 (18) | C3—C3A—C7A—N7 | 175.66 (18) |
C3A—C4—C5—C6 | −2.6 (3) | C4—C3A—C7A—N1 | −177.08 (16) |
C41—C4—C5—C6 | 178.20 (17) | C3—C3A—C7A—N1 | −1.9 (2) |
C3A—C4—C5—C51 | 176.79 (17) | C22—N20—C20—O20 | −1.5 (3) |
C41—C4—C5—C51 | −2.4 (3) | C21—N20—C20—O20 | 177.6 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N63—H63···O20 | 0.88 | 1.89 | 2.767 (2) | 173 |
C42—H42···Cgi | 0.95 | 2.65 | 3.514 (2) | 151 |
Symmetry code: (i) −x+1, −y+1, −z+1. |
(II) 6-(1
H-indol-3-yl)-3-methyl-4-(4-methoxyphenyl)-1-phenyl-1
H-
pyrazolo[3,4-
b]pyridine-5-carbonitrile
top
Crystal data top
C29H21N5O·C3H7NO | F(000) = 2224 |
Mr = 528.60 | Dx = 1.330 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 6055 reflections |
a = 30.303 (3) Å | θ = 3.8–27.5° |
b = 11.3490 (16) Å | µ = 0.09 mm−1 |
c = 20.344 (3) Å | T = 120 K |
β = 131.010 (5)° | Block, colourless |
V = 5279.5 (12) Å3 | 0.51 × 0.49 × 0.27 mm |
Z = 8 | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 6055 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 3416 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.074 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.8° |
ϕ & ω scans | h = −39→39 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −14→14 |
Tmin = 0.949, Tmax = 0.977 | l = −26→26 |
63662 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.069 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.237 | H-atom parameters constrained |
S = 1.07 | w = 1/[σ2(Fo2) + (0.1316P)2 + 4.8045P] where P = (Fo2 + 2Fc2)/3 |
6055 reflections | (Δ/σ)max < 0.001 |
365 parameters | Δρmax = 0.43 e Å−3 |
0 restraints | Δρmin = −0.34 e Å−3 |
Crystal data top
C29H21N5O·C3H7NO | V = 5279.5 (12) Å3 |
Mr = 528.60 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 30.303 (3) Å | µ = 0.09 mm−1 |
b = 11.3490 (16) Å | T = 120 K |
c = 20.344 (3) Å | 0.51 × 0.49 × 0.27 mm |
β = 131.010 (5)° | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 6055 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3416 reflections with I > 2σ(I) |
Tmin = 0.949, Tmax = 0.977 | Rint = 0.074 |
63662 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.237 | H-atom parameters constrained |
S = 1.07 | Δρmax = 0.43 e Å−3 |
6055 reflections | Δρmin = −0.34 e Å−3 |
365 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.32488 (10) | 0.7888 (2) | 0.70486 (14) | 0.0322 (5) | |
C11 | 0.36448 (12) | 0.8849 (2) | 0.73863 (17) | 0.0321 (6) | |
C12 | 0.38321 (13) | 0.9405 (3) | 0.81386 (18) | 0.0380 (7) | |
C13 | 0.42035 (13) | 1.0364 (3) | 0.8457 (2) | 0.0435 (8) | |
C14 | 0.43968 (13) | 1.0772 (3) | 0.80465 (19) | 0.0401 (7) | |
C15 | 0.42110 (12) | 1.0207 (3) | 0.72984 (19) | 0.0385 (7) | |
C16 | 0.38351 (11) | 0.9253 (2) | 0.69623 (18) | 0.0333 (6) | |
N2 | 0.29659 (10) | 0.7677 (2) | 0.73639 (15) | 0.0343 (6) | |
C3 | 0.25999 (12) | 0.6793 (3) | 0.69113 (18) | 0.0336 (6) | |
C31 | 0.22399 (13) | 0.6345 (3) | 0.71148 (19) | 0.0400 (7) | |
C3A | 0.26325 (11) | 0.6392 (2) | 0.62731 (17) | 0.0304 (6) | |
C4 | 0.23864 (11) | 0.5493 (2) | 0.56523 (17) | 0.0300 (6) | |
C41 | 0.19147 (11) | 0.4709 (2) | 0.54415 (17) | 0.0297 (6) | |
C42 | 0.13762 (12) | 0.5176 (2) | 0.51039 (17) | 0.0326 (6) | |
C43 | 0.09360 (12) | 0.4440 (2) | 0.48931 (18) | 0.0330 (6) | |
C44 | 0.10316 (11) | 0.3233 (2) | 0.50422 (17) | 0.0306 (6) | |
O44 | 0.05704 (8) | 0.25804 (17) | 0.48253 (13) | 0.0379 (5) | |
C441 | 0.06882 (14) | 0.1363 (3) | 0.5079 (2) | 0.0418 (7) | |
C45 | 0.15661 (12) | 0.2763 (3) | 0.53807 (18) | 0.0336 (6) | |
C46 | 0.20003 (12) | 0.3501 (2) | 0.55714 (18) | 0.0331 (6) | |
C5 | 0.26140 (11) | 0.5367 (2) | 0.52369 (17) | 0.0297 (6) | |
C51 | 0.23897 (12) | 0.4441 (3) | 0.46091 (19) | 0.0326 (6) | |
N51 | 0.22104 (10) | 0.3701 (2) | 0.41031 (16) | 0.0383 (6) | |
C6 | 0.30551 (11) | 0.6147 (2) | 0.54193 (16) | 0.0285 (6) | |
C61 | 0.33029 (11) | 0.6076 (2) | 0.49971 (17) | 0.0287 (6) | |
C62 | 0.30427 (12) | 0.5661 (2) | 0.41748 (18) | 0.0324 (6) | |
N63 | 0.33872 (10) | 0.5905 (2) | 0.39853 (15) | 0.0336 (6) | |
C63A | 0.38834 (12) | 0.6484 (2) | 0.46756 (18) | 0.0305 (6) | |
C64 | 0.43473 (12) | 0.6915 (3) | 0.47644 (19) | 0.0343 (6) | |
C65 | 0.47972 (12) | 0.7480 (3) | 0.55343 (19) | 0.0356 (7) | |
C66 | 0.47790 (12) | 0.7598 (2) | 0.62011 (18) | 0.0342 (6) | |
C67 | 0.43153 (12) | 0.7167 (2) | 0.61128 (17) | 0.0313 (6) | |
C67A | 0.38476 (11) | 0.6605 (2) | 0.53326 (17) | 0.0281 (6) | |
N7 | 0.32761 (9) | 0.7014 (2) | 0.60023 (14) | 0.0302 (5) | |
C7A | 0.30613 (11) | 0.7103 (2) | 0.64019 (17) | 0.0293 (6) | |
N20 | 0.39941 (11) | 0.5910 (2) | 0.22693 (15) | 0.0388 (6) | |
C20 | 0.36099 (14) | 0.6152 (3) | 0.2364 (2) | 0.0433 (8) | |
O20 | 0.35567 (11) | 0.5587 (2) | 0.28208 (15) | 0.0576 (7) | |
C21 | 0.40002 (17) | 0.6580 (3) | 0.1665 (2) | 0.0554 (9) | |
C22 | 0.44024 (16) | 0.4946 (3) | 0.2732 (2) | 0.0553 (9) | |
H12 | 0.3706 | 0.9130 | 0.8433 | 0.046* | |
H13 | 0.4328 | 1.0749 | 0.8969 | 0.052* | |
H14 | 0.4653 | 1.1430 | 0.8272 | 0.048* | |
H15 | 0.4344 | 1.0478 | 0.7012 | 0.046* | |
H16 | 0.3708 | 0.8876 | 0.6446 | 0.040* | |
H31A | 0.2379 | 0.6693 | 0.7663 | 0.060* | |
H31B | 0.2274 | 0.5485 | 0.7172 | 0.060* | |
H31C | 0.1830 | 0.6561 | 0.6644 | 0.060* | |
H42 | 0.1312 | 0.6002 | 0.5019 | 0.039* | |
H43 | 0.0566 | 0.4760 | 0.4645 | 0.040* | |
H44A | 0.0806 | 0.0962 | 0.4789 | 0.063* | |
H44B | 0.0335 | 0.0989 | 0.4909 | 0.063* | |
H44C | 0.1004 | 0.1306 | 0.5712 | 0.063* | |
H45 | 0.1634 | 0.1939 | 0.5481 | 0.040* | |
H46 | 0.2364 | 0.3174 | 0.5796 | 0.040* | |
H62 | 0.2677 | 0.5264 | 0.3799 | 0.039* | |
H63 | 0.3306 | 0.5722 | 0.3495 | 0.040* | |
H64 | 0.4357 | 0.6827 | 0.4310 | 0.041* | |
H65 | 0.5119 | 0.7788 | 0.5610 | 0.043* | |
H66 | 0.5092 | 0.7982 | 0.6726 | 0.041* | |
H67 | 0.4312 | 0.7250 | 0.6575 | 0.038* | |
H20 | 0.3359 | 0.6810 | 0.2056 | 0.052* | |
H21A | 0.3698 | 0.7191 | 0.1387 | 0.083* | |
H21B | 0.3923 | 0.6050 | 0.1219 | 0.083* | |
H21C | 0.4384 | 0.6950 | 0.1984 | 0.083* | |
H22A | 0.4322 | 0.4515 | 0.3061 | 0.083* | |
H22B | 0.4802 | 0.5256 | 0.3134 | 0.083* | |
H22C | 0.4360 | 0.4412 | 0.2314 | 0.083* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0328 (12) | 0.0364 (13) | 0.0322 (12) | 0.0006 (10) | 0.0234 (11) | −0.0011 (10) |
C11 | 0.0274 (13) | 0.0316 (15) | 0.0300 (14) | 0.0039 (11) | 0.0157 (12) | −0.0014 (12) |
C12 | 0.0391 (16) | 0.0396 (17) | 0.0346 (15) | −0.0002 (14) | 0.0239 (14) | −0.0037 (13) |
C13 | 0.0411 (17) | 0.0433 (19) | 0.0366 (16) | −0.0018 (14) | 0.0214 (14) | −0.0085 (14) |
C14 | 0.0374 (16) | 0.0315 (16) | 0.0389 (16) | −0.0026 (13) | 0.0196 (14) | −0.0047 (13) |
C15 | 0.0367 (15) | 0.0354 (17) | 0.0420 (17) | −0.0012 (13) | 0.0253 (14) | −0.0035 (13) |
C16 | 0.0304 (14) | 0.0339 (15) | 0.0311 (14) | 0.0002 (12) | 0.0183 (13) | −0.0042 (12) |
N2 | 0.0355 (13) | 0.0396 (14) | 0.0329 (13) | −0.0002 (11) | 0.0247 (11) | −0.0006 (11) |
C3 | 0.0344 (15) | 0.0365 (16) | 0.0325 (15) | 0.0033 (13) | 0.0230 (13) | 0.0032 (12) |
C31 | 0.0442 (17) | 0.0454 (18) | 0.0376 (16) | −0.0009 (14) | 0.0300 (15) | −0.0015 (14) |
C3A | 0.0308 (14) | 0.0335 (15) | 0.0290 (14) | 0.0036 (12) | 0.0205 (12) | 0.0030 (11) |
C4 | 0.0287 (13) | 0.0304 (15) | 0.0295 (14) | 0.0043 (11) | 0.0185 (12) | 0.0053 (11) |
C41 | 0.0291 (13) | 0.0317 (15) | 0.0277 (13) | 0.0006 (11) | 0.0183 (12) | 0.0012 (11) |
C42 | 0.0390 (15) | 0.0281 (14) | 0.0333 (15) | 0.0023 (12) | 0.0249 (13) | 0.0029 (12) |
C43 | 0.0307 (14) | 0.0327 (15) | 0.0367 (15) | 0.0034 (12) | 0.0226 (13) | 0.0029 (12) |
C44 | 0.0323 (14) | 0.0325 (15) | 0.0316 (14) | 0.0002 (12) | 0.0230 (13) | 0.0024 (11) |
O44 | 0.0351 (11) | 0.0302 (11) | 0.0532 (13) | 0.0016 (9) | 0.0310 (10) | 0.0069 (9) |
C441 | 0.0469 (17) | 0.0289 (15) | 0.0582 (19) | −0.0007 (13) | 0.0382 (16) | 0.0050 (14) |
C45 | 0.0375 (15) | 0.0295 (15) | 0.0371 (15) | 0.0043 (12) | 0.0260 (14) | 0.0032 (12) |
C46 | 0.0293 (14) | 0.0339 (16) | 0.0342 (15) | 0.0010 (12) | 0.0200 (13) | 0.0017 (12) |
C5 | 0.0297 (14) | 0.0293 (14) | 0.0292 (14) | 0.0043 (11) | 0.0190 (12) | 0.0021 (11) |
C51 | 0.0304 (14) | 0.0312 (15) | 0.0374 (15) | 0.0002 (12) | 0.0228 (13) | 0.0000 (13) |
N51 | 0.0365 (13) | 0.0339 (14) | 0.0443 (14) | −0.0006 (11) | 0.0264 (12) | −0.0045 (12) |
C6 | 0.0252 (13) | 0.0290 (14) | 0.0283 (13) | 0.0039 (11) | 0.0163 (12) | 0.0021 (11) |
C61 | 0.0305 (14) | 0.0285 (14) | 0.0293 (13) | 0.0020 (11) | 0.0205 (12) | −0.0007 (11) |
C62 | 0.0339 (15) | 0.0297 (15) | 0.0379 (15) | −0.0012 (12) | 0.0254 (13) | −0.0009 (12) |
N63 | 0.0353 (13) | 0.0357 (13) | 0.0325 (12) | −0.0019 (10) | 0.0235 (11) | −0.0037 (10) |
C63A | 0.0356 (15) | 0.0246 (14) | 0.0349 (15) | 0.0030 (12) | 0.0246 (13) | 0.0019 (11) |
C64 | 0.0351 (15) | 0.0357 (16) | 0.0387 (15) | −0.0011 (12) | 0.0272 (14) | −0.0006 (13) |
C65 | 0.0358 (15) | 0.0311 (15) | 0.0426 (16) | 0.0006 (12) | 0.0269 (14) | 0.0026 (13) |
C66 | 0.0310 (14) | 0.0297 (15) | 0.0358 (15) | −0.0021 (12) | 0.0194 (13) | −0.0019 (12) |
C67 | 0.0351 (14) | 0.0300 (15) | 0.0319 (14) | 0.0034 (12) | 0.0233 (13) | 0.0028 (11) |
C67A | 0.0292 (14) | 0.0250 (13) | 0.0302 (14) | 0.0031 (11) | 0.0195 (12) | 0.0034 (11) |
N7 | 0.0312 (12) | 0.0300 (12) | 0.0309 (12) | 0.0009 (10) | 0.0210 (11) | −0.0022 (10) |
C7A | 0.0291 (13) | 0.0287 (14) | 0.0278 (13) | 0.0030 (11) | 0.0176 (12) | −0.0006 (11) |
N20 | 0.0413 (14) | 0.0418 (15) | 0.0374 (13) | 0.0034 (11) | 0.0276 (12) | 0.0005 (11) |
C20 | 0.0427 (17) | 0.051 (2) | 0.0362 (16) | −0.0015 (15) | 0.0260 (15) | −0.0072 (14) |
O20 | 0.0665 (16) | 0.0723 (17) | 0.0502 (14) | −0.0131 (13) | 0.0454 (13) | −0.0142 (12) |
C21 | 0.070 (2) | 0.054 (2) | 0.059 (2) | −0.0045 (18) | 0.049 (2) | −0.0024 (18) |
C22 | 0.057 (2) | 0.047 (2) | 0.055 (2) | 0.0131 (17) | 0.0340 (18) | −0.0009 (17) |
Geometric parameters (Å, º) top
N1—C7A | 1.366 (3) | C45—C46 | 1.383 (4) |
N1—N2 | 1.388 (3) | C45—H45 | 0.95 |
N1—C11 | 1.421 (4) | C46—H46 | 0.95 |
C11—C12 | 1.387 (4) | C5—C6 | 1.435 (4) |
C11—C16 | 1.393 (4) | C5—C51 | 1.435 (4) |
C12—C13 | 1.384 (4) | C51—N51 | 1.151 (3) |
C12—H12 | 0.95 | C6—N7 | 1.335 (3) |
C13—C14 | 1.377 (5) | C6—C61 | 1.468 (4) |
C13—H13 | 0.95 | C61—C62 | 1.383 (4) |
C14—C15 | 1.386 (4) | C61—C67A | 1.439 (4) |
C14—H14 | 0.95 | C62—N63 | 1.358 (3) |
C15—C16 | 1.384 (4) | C62—H62 | 0.95 |
C15—H15 | 0.95 | N63—C63A | 1.376 (4) |
C16—H16 | 0.95 | N63—H63 | 0.88 |
N2—C3 | 1.321 (4) | C63A—C64 | 1.384 (4) |
C3—C3A | 1.439 (4) | C63A—C67A | 1.417 (4) |
C3—C31 | 1.487 (4) | C64—C65 | 1.386 (4) |
C31—H31A | 0.98 | C64—H64 | 0.95 |
C31—H31B | 0.98 | C65—C66 | 1.400 (4) |
C31—H31C | 0.98 | C65—H65 | 0.95 |
C3A—C4 | 1.399 (4) | C66—C67 | 1.384 (4) |
C3A—C7A | 1.400 (4) | C66—H66 | 0.95 |
C4—C5 | 1.405 (4) | C67—C67A | 1.408 (4) |
C4—C41 | 1.488 (4) | C67—H67 | 0.95 |
C41—C46 | 1.388 (4) | N7—C7A | 1.338 (3) |
C41—C42 | 1.395 (4) | N20—C20 | 1.328 (4) |
C42—C43 | 1.382 (4) | N20—C22 | 1.444 (4) |
C42—H42 | 0.95 | N20—C21 | 1.455 (4) |
C43—C44 | 1.392 (4) | C20—O20 | 1.223 (4) |
C43—H43 | 0.95 | C20—H20 | 0.95 |
C44—O44 | 1.374 (3) | C21—H21A | 0.98 |
C44—C45 | 1.385 (4) | C21—H21B | 0.98 |
O44—C441 | 1.436 (3) | C21—H21C | 0.98 |
C441—H44A | 0.98 | C22—H22A | 0.98 |
C441—H44B | 0.98 | C22—H22B | 0.98 |
C441—H44C | 0.98 | C22—H22C | 0.98 |
| | | |
C7A—N1—N2 | 109.9 (2) | C45—C46—C41 | 121.3 (3) |
C7A—N1—C11 | 130.7 (2) | C45—C46—H46 | 119.3 |
N2—N1—C11 | 119.4 (2) | C41—C46—H46 | 119.3 |
C12—C11—C16 | 119.8 (3) | C4—C5—C6 | 121.5 (2) |
C12—C11—N1 | 119.2 (3) | C4—C5—C51 | 118.5 (2) |
C16—C11—N1 | 121.0 (2) | C6—C5—C51 | 119.9 (2) |
C13—C12—C11 | 119.5 (3) | N51—C51—C5 | 179.6 (3) |
C13—C12—H12 | 120.2 | N7—C6—C5 | 121.6 (2) |
C11—C12—H12 | 120.2 | N7—C6—C61 | 114.2 (2) |
C14—C13—C12 | 121.3 (3) | C5—C6—C61 | 124.2 (2) |
C14—C13—H13 | 119.3 | C62—C61—C67A | 106.4 (2) |
C12—C13—H13 | 119.3 | C62—C61—C6 | 128.5 (2) |
C13—C14—C15 | 118.8 (3) | C67A—C61—C6 | 124.6 (2) |
C13—C14—H14 | 120.6 | N63—C62—C61 | 109.9 (2) |
C15—C14—H14 | 120.6 | N63—C62—H62 | 125.1 |
C16—C15—C14 | 121.0 (3) | C61—C62—H62 | 125.1 |
C16—C15—H15 | 119.5 | C62—N63—C63A | 109.7 (2) |
C14—C15—H15 | 119.5 | C62—N63—H63 | 125.2 |
C15—C16—C11 | 119.5 (3) | C63A—N63—H63 | 125.2 |
C15—C16—H16 | 120.2 | N63—C63A—C64 | 129.7 (3) |
C11—C16—H16 | 120.2 | N63—C63A—C67A | 107.5 (2) |
C3—N2—N1 | 107.4 (2) | C64—C63A—C67A | 122.9 (3) |
N2—C3—C3A | 110.2 (2) | C63A—C64—C65 | 118.2 (3) |
N2—C3—C31 | 119.9 (2) | C63A—C64—H64 | 120.9 |
C3A—C3—C31 | 129.8 (3) | C65—C64—H64 | 120.9 |
C3—C31—H31A | 109.5 | C64—C65—C66 | 120.3 (3) |
C3—C31—H31B | 109.5 | C64—C65—H65 | 119.8 |
H31A—C31—H31B | 109.5 | C66—C65—H65 | 119.8 |
C3—C31—H31C | 109.5 | C67—C66—C65 | 121.5 (3) |
H31A—C31—H31C | 109.5 | C67—C66—H66 | 119.2 |
H31B—C31—H31C | 109.5 | C65—C66—H66 | 119.2 |
C4—C3A—C7A | 117.9 (2) | C66—C67—C67A | 119.5 (2) |
C4—C3A—C3 | 137.2 (3) | C66—C67—H67 | 120.3 |
C7A—C3A—C3 | 104.7 (2) | C67A—C67—H67 | 120.3 |
C3A—C4—C5 | 115.8 (2) | C67—C67A—C63A | 117.6 (2) |
C3A—C4—C41 | 122.6 (2) | C67—C67A—C61 | 135.7 (2) |
C5—C4—C41 | 121.6 (2) | C63A—C67A—C61 | 106.6 (2) |
C46—C41—C42 | 118.8 (3) | C6—N7—C7A | 115.8 (2) |
C46—C41—C4 | 120.8 (2) | N7—C7A—N1 | 125.0 (2) |
C42—C41—C4 | 120.5 (2) | N7—C7A—C3A | 127.2 (2) |
C43—C42—C41 | 120.1 (3) | N1—C7A—C3A | 107.7 (2) |
C43—C42—H42 | 119.9 | C20—N20—C22 | 121.3 (3) |
C41—C42—H42 | 119.9 | C20—N20—C21 | 120.8 (3) |
C42—C43—C44 | 120.5 (3) | C22—N20—C21 | 117.8 (3) |
C42—C43—H43 | 119.8 | O20—C20—N20 | 124.5 (3) |
C44—C43—H43 | 119.8 | O20—C20—H20 | 117.8 |
O44—C44—C45 | 124.3 (3) | N20—C20—H20 | 117.8 |
O44—C44—C43 | 116.0 (2) | N20—C21—H21A | 109.5 |
C45—C44—C43 | 119.7 (3) | N20—C21—H21B | 109.5 |
C44—O44—C441 | 116.3 (2) | H21A—C21—H21B | 109.5 |
O44—C441—H44A | 109.5 | N20—C21—H21C | 109.5 |
O44—C441—H44B | 109.5 | H21A—C21—H21C | 109.5 |
H44A—C441—H44B | 109.5 | H21B—C21—H21C | 109.5 |
O44—C441—H44C | 109.5 | N20—C22—H22A | 109.5 |
H44A—C441—H44C | 109.5 | N20—C22—H22B | 109.5 |
H44B—C441—H44C | 109.5 | H22A—C22—H22B | 109.5 |
C46—C45—C44 | 119.5 (3) | N20—C22—H22C | 109.5 |
C46—C45—H45 | 120.2 | H22A—C22—H22C | 109.5 |
C44—C45—H45 | 120.2 | H22B—C22—H22C | 109.5 |
| | | |
C7A—N1—C11—C12 | −170.2 (3) | C41—C4—C5—C51 | −1.3 (4) |
N2—N1—C11—C12 | 13.1 (4) | C4—C5—C6—N7 | 1.2 (4) |
C7A—N1—C11—C16 | 11.3 (4) | C51—C5—C6—N7 | −179.6 (2) |
N2—N1—C11—C16 | −165.4 (2) | C4—C5—C6—C61 | −178.8 (2) |
C16—C11—C12—C13 | 0.5 (4) | C51—C5—C6—C61 | 0.3 (4) |
N1—C11—C12—C13 | −178.0 (3) | N7—C6—C61—C62 | −151.4 (3) |
C11—C12—C13—C14 | −0.7 (5) | C5—C6—C61—C62 | 28.6 (4) |
C12—C13—C14—C15 | 0.2 (5) | N7—C6—C61—C67A | 18.7 (4) |
C13—C14—C15—C16 | 0.4 (5) | C5—C6—C61—C67A | −161.3 (3) |
C14—C15—C16—C11 | −0.6 (4) | C67A—C61—C62—N63 | −0.4 (3) |
C12—C11—C16—C15 | 0.1 (4) | C6—C61—C62—N63 | 171.1 (3) |
N1—C11—C16—C15 | 178.6 (2) | C61—C62—N63—C63A | 0.2 (3) |
C7A—N1—N2—C3 | −1.2 (3) | C62—N63—C63A—C64 | −178.8 (3) |
C11—N1—N2—C3 | 176.2 (2) | C62—N63—C63A—C67A | 0.1 (3) |
N1—N2—C3—C3A | −0.1 (3) | N63—C63A—C64—C65 | 179.4 (3) |
N1—N2—C3—C31 | 178.7 (2) | C67A—C63A—C64—C65 | 0.6 (4) |
N2—C3—C3A—C4 | 176.4 (3) | C63A—C64—C65—C66 | 0.4 (4) |
C31—C3—C3A—C4 | −2.3 (5) | C64—C65—C66—C67 | −0.5 (4) |
N2—C3—C3A—C7A | 1.3 (3) | C65—C66—C67—C67A | −0.5 (4) |
C31—C3—C3A—C7A | −177.4 (3) | C66—C67—C67A—C63A | 1.4 (4) |
C7A—C3A—C4—C5 | 2.2 (4) | C66—C67—C67A—C61 | −178.8 (3) |
C3—C3A—C4—C5 | −172.4 (3) | N63—C63A—C67A—C67 | 179.4 (2) |
C7A—C3A—C4—C41 | −178.0 (2) | C64—C63A—C67A—C67 | −1.5 (4) |
C3—C3A—C4—C41 | 7.3 (5) | N63—C63A—C67A—C61 | −0.4 (3) |
C3A—C4—C41—C46 | −119.0 (3) | C64—C63A—C67A—C61 | 178.7 (2) |
C5—C4—C41—C46 | 60.7 (4) | C62—C61—C67A—C67 | −179.3 (3) |
C3A—C4—C41—C42 | 61.4 (4) | C6—C61—C67A—C67 | 8.8 (5) |
C5—C4—C41—C42 | −118.9 (3) | C62—C61—C67A—C63A | 0.5 (3) |
C46—C41—C42—C43 | −0.9 (4) | C6—C61—C67A—C63A | −171.5 (2) |
C4—C41—C42—C43 | 178.7 (2) | C5—C6—N7—C7A | 0.2 (4) |
C41—C42—C43—C44 | 2.2 (4) | C61—C6—N7—C7A | −179.8 (2) |
C42—C43—C44—O44 | 178.8 (2) | C6—N7—C7A—N1 | 176.5 (2) |
C42—C43—C44—C45 | −1.9 (4) | C6—N7—C7A—C3A | −0.2 (4) |
C45—C44—O44—C441 | 8.5 (4) | N2—N1—C7A—N7 | −175.2 (2) |
C43—C44—O44—C441 | −172.3 (2) | C11—N1—C7A—N7 | 7.8 (4) |
O44—C44—C45—C46 | 179.6 (2) | N2—N1—C7A—C3A | 2.0 (3) |
C43—C44—C45—C46 | 0.4 (4) | C11—N1—C7A—C3A | −174.9 (3) |
C44—C45—C46—C41 | 0.9 (4) | C4—C3A—C7A—N7 | −1.0 (4) |
C42—C41—C46—C45 | −0.6 (4) | C3—C3A—C7A—N7 | 175.2 (3) |
C4—C41—C46—C45 | 179.8 (2) | C4—C3A—C7A—N1 | −178.2 (2) |
C3A—C4—C5—C6 | −2.3 (4) | C3—C3A—C7A—N1 | −2.0 (3) |
C41—C4—C5—C6 | 177.9 (2) | C22—N20—C20—O20 | −1.7 (5) |
C3A—C4—C5—C51 | 178.5 (2) | C21—N20—C20—O20 | 175.7 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N63—H63···O20 | 0.88 | 1.96 | 2.758 (3) | 149 |
C42—H42···Cgi | 0.95 | 2.68 | 3.558 (3) | 154 |
C46—H46···N51ii | 0.95 | 2.43 | 3.213 (4) | 140 |
Symmetry codes: (i) −x+1/2, −y+3/2, −z+1; (ii) −x+1/2, −y+1/2, −z+1. |
(III) 6-(1
H-indol-3-yl)-3-methyl-1-phenyl-4-(3,4,5-trimethoxyphenyl)-1
H-
pyrazolo[3,4-
b]pyridine-5-carbonitrile
top
Crystal data top
C31H25N5O3 | Z = 2 |
Mr = 515.56 | F(000) = 540 |
Triclinic, P1 | Dx = 1.346 Mg m−3 |
Hall symbol: -P 1 | Mo Kα radiation, λ = 0.71073 Å |
a = 8.8241 (10) Å | Cell parameters from 5825 reflections |
b = 11.9901 (9) Å | θ = 3.1–27.5° |
c = 12.9130 (17) Å | µ = 0.09 mm−1 |
α = 99.372 (9)° | T = 120 K |
β = 108.822 (12)° | Block, colourless |
γ = 90.994 (7)° | 0.38 × 0.20 × 0.18 mm |
V = 1272.3 (3) Å3 | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 5825 independent reflections |
Radiation source: Bruker–Nonius FR591 rotating anode | 3165 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.075 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.1° |
ϕ & ω scans | h = −11→11 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −15→15 |
Tmin = 0.960, Tmax = 0.984 | l = −16→16 |
31225 measured reflections | |
Refinement top
Refinement on F2 | Primary atom site location: structure-invariant direct methods |
Least-squares matrix: full | Secondary atom site location: difference Fourier map |
R[F2 > 2σ(F2)] = 0.055 | Hydrogen site location: inferred from neighbouring sites |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 1.06 | w = 1/[σ2(Fo2) + (0.0677P)2 + 0.2687P] where P = (Fo2 + 2Fc2)/3 |
5825 reflections | (Δ/σ)max = 0.001 |
356 parameters | Δρmax = 0.27 e Å−3 |
0 restraints | Δρmin = −0.35 e Å−3 |
Crystal data top
C31H25N5O3 | γ = 90.994 (7)° |
Mr = 515.56 | V = 1272.3 (3) Å3 |
Triclinic, P1 | Z = 2 |
a = 8.8241 (10) Å | Mo Kα radiation |
b = 11.9901 (9) Å | µ = 0.09 mm−1 |
c = 12.9130 (17) Å | T = 120 K |
α = 99.372 (9)° | 0.38 × 0.20 × 0.18 mm |
β = 108.822 (12)° | |
Data collection top
Bruker–Nonius KappaCCD diffractometer | 5825 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3165 reflections with I > 2σ(I) |
Tmin = 0.960, Tmax = 0.984 | Rint = 0.075 |
31225 measured reflections | |
Refinement top
R[F2 > 2σ(F2)] = 0.055 | 0 restraints |
wR(F2) = 0.152 | H-atom parameters constrained |
S = 1.06 | Δρmax = 0.27 e Å−3 |
5825 reflections | Δρmin = −0.35 e Å−3 |
356 parameters | |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
N1 | 0.8288 (2) | 0.55082 (15) | 0.57478 (15) | 0.0208 (4) | |
C11 | 0.9416 (3) | 0.49719 (18) | 0.65428 (18) | 0.0211 (5) | |
C12 | 0.9807 (3) | 0.5419 (2) | 0.76630 (19) | 0.0263 (6) | |
C13 | 1.0826 (3) | 0.4863 (2) | 0.8447 (2) | 0.0325 (6) | |
C14 | 1.1465 (3) | 0.3881 (2) | 0.8109 (2) | 0.0310 (6) | |
C15 | 1.1108 (3) | 0.3464 (2) | 0.6982 (2) | 0.0266 (6) | |
C16 | 1.0081 (3) | 0.40045 (19) | 0.61969 (19) | 0.0227 (5) | |
N2 | 0.8238 (2) | 0.66726 (15) | 0.59466 (15) | 0.0228 (5) | |
C3 | 0.7047 (3) | 0.69342 (18) | 0.51153 (19) | 0.0217 (5) | |
C31 | 0.6765 (3) | 0.81545 (18) | 0.5070 (2) | 0.0275 (6) | |
C3A | 0.6254 (3) | 0.59281 (18) | 0.43482 (18) | 0.0188 (5) | |
C4 | 0.5023 (3) | 0.56642 (18) | 0.33228 (18) | 0.0191 (5) | |
C41 | 0.4069 (2) | 0.65372 (17) | 0.27670 (18) | 0.0183 (5) | |
C42 | 0.3253 (3) | 0.72433 (18) | 0.33320 (19) | 0.0208 (5) | |
C43 | 0.2327 (3) | 0.80450 (18) | 0.28112 (18) | 0.0194 (5) | |
O43 | 0.14951 (19) | 0.87919 (13) | 0.32893 (13) | 0.0271 (4) | |
C431 | 0.1773 (3) | 0.8859 (2) | 0.44543 (19) | 0.0302 (6) | |
C44 | 0.2193 (3) | 0.81218 (18) | 0.17206 (18) | 0.0210 (5) | |
O44 | 0.13111 (18) | 0.89568 (12) | 0.12391 (13) | 0.0256 (4) | |
C441 | −0.0060 (3) | 0.8548 (2) | 0.0261 (2) | 0.0355 (7) | |
C45 | 0.3052 (3) | 0.74285 (19) | 0.11722 (18) | 0.0221 (5) | |
O45 | 0.29257 (19) | 0.76236 (14) | 0.01335 (13) | 0.0310 (4) | |
C451 | 0.4007 (3) | 0.7087 (2) | −0.0378 (2) | 0.0353 (6) | |
C46 | 0.3984 (3) | 0.66287 (18) | 0.16897 (18) | 0.0206 (5) | |
C5 | 0.4756 (3) | 0.45107 (18) | 0.28397 (18) | 0.0196 (5) | |
C51 | 0.3603 (3) | 0.41607 (18) | 0.1744 (2) | 0.0214 (5) | |
N51 | 0.2724 (2) | 0.38747 (16) | 0.08551 (17) | 0.0309 (5) | |
C6 | 0.5638 (3) | 0.36616 (18) | 0.33867 (18) | 0.0195 (5) | |
C61 | 0.5269 (3) | 0.24616 (18) | 0.29019 (18) | 0.0208 (5) | |
C62 | 0.3775 (3) | 0.18915 (18) | 0.24427 (18) | 0.0235 (5) | |
N63 | 0.3908 (2) | 0.07754 (15) | 0.20989 (16) | 0.0272 (5) | |
C63A | 0.5513 (3) | 0.05854 (19) | 0.23097 (19) | 0.0244 (5) | |
C64 | 0.6229 (3) | −0.0399 (2) | 0.2067 (2) | 0.0326 (6) | |
C65 | 0.7872 (3) | −0.0324 (2) | 0.2320 (2) | 0.0349 (7) | |
C66 | 0.8778 (3) | 0.0711 (2) | 0.2787 (2) | 0.0293 (6) | |
C67 | 0.8076 (3) | 0.16856 (19) | 0.30425 (19) | 0.0244 (5) | |
C67A | 0.6411 (3) | 0.16309 (18) | 0.28160 (18) | 0.0214 (5) | |
N7 | 0.6836 (2) | 0.39235 (15) | 0.43588 (15) | 0.0207 (4) | |
C7A | 0.7109 (3) | 0.50362 (18) | 0.47888 (18) | 0.0190 (5) | |
H12 | 0.9380 | 0.6101 | 0.7894 | 0.032* | |
H13 | 1.1084 | 0.5159 | 0.9217 | 0.039* | |
H14 | 1.2145 | 0.3493 | 0.8645 | 0.037* | |
H15 | 1.1574 | 0.2802 | 0.6748 | 0.032* | |
H16 | 0.9834 | 0.3714 | 0.5427 | 0.027* | |
H31A | 0.5802 | 0.8338 | 0.5265 | 0.041* | |
H31B | 0.6615 | 0.8293 | 0.4317 | 0.041* | |
H31C | 0.7693 | 0.8632 | 0.5599 | 0.041* | |
H42 | 0.3328 | 0.7179 | 0.4070 | 0.025* | |
H43A | 0.1513 | 0.8114 | 0.4598 | 0.045* | |
H43B | 0.1092 | 0.9411 | 0.4692 | 0.045* | |
H43C | 0.2904 | 0.9099 | 0.4870 | 0.045* | |
H44A | 0.0278 | 0.8442 | −0.0399 | 0.053* | |
H44B | −0.0874 | 0.9103 | 0.0186 | 0.053* | |
H44C | −0.0512 | 0.7824 | 0.0332 | 0.053* | |
H45A | 0.5116 | 0.7314 | 0.0102 | 0.053* | |
H45B | 0.3831 | 0.7318 | −0.1099 | 0.053* | |
H45C | 0.3815 | 0.6262 | −0.0486 | 0.053* | |
H46 | 0.4557 | 0.6149 | 0.1313 | 0.025* | |
H62 | 0.2790 | 0.2229 | 0.2375 | 0.028* | |
H63 | 0.3101 | 0.0256 | 0.1791 | 0.033* | |
H64 | 0.5608 | −0.1099 | 0.1737 | 0.039* | |
H65 | 0.8398 | −0.0987 | 0.2176 | 0.042* | |
H66 | 0.9905 | 0.0741 | 0.2931 | 0.035* | |
H67 | 0.8708 | 0.2382 | 0.3366 | 0.029* | |
Atomic displacement parameters (Å2) top | U11 | U22 | U33 | U12 | U13 | U23 |
N1 | 0.0214 (10) | 0.0175 (10) | 0.0211 (10) | 0.0033 (8) | 0.0030 (8) | 0.0043 (8) |
C11 | 0.0175 (12) | 0.0221 (12) | 0.0232 (13) | 0.0003 (10) | 0.0052 (10) | 0.0060 (10) |
C12 | 0.0236 (13) | 0.0263 (13) | 0.0258 (13) | 0.0053 (11) | 0.0047 (11) | 0.0021 (11) |
C13 | 0.0327 (15) | 0.0419 (16) | 0.0172 (13) | 0.0042 (12) | 0.0015 (11) | 0.0024 (11) |
C14 | 0.0245 (14) | 0.0363 (15) | 0.0298 (15) | 0.0036 (11) | 0.0033 (11) | 0.0112 (12) |
C15 | 0.0214 (13) | 0.0296 (14) | 0.0301 (14) | 0.0049 (11) | 0.0079 (11) | 0.0099 (11) |
C16 | 0.0228 (13) | 0.0252 (13) | 0.0209 (12) | 0.0007 (10) | 0.0084 (10) | 0.0040 (10) |
N2 | 0.0242 (11) | 0.0191 (10) | 0.0250 (11) | 0.0011 (8) | 0.0080 (9) | 0.0037 (8) |
C3 | 0.0215 (13) | 0.0221 (13) | 0.0218 (12) | 0.0029 (10) | 0.0072 (10) | 0.0045 (10) |
C31 | 0.0298 (14) | 0.0192 (12) | 0.0272 (14) | −0.0004 (10) | 0.0021 (11) | 0.0016 (10) |
C3A | 0.0193 (12) | 0.0165 (12) | 0.0220 (12) | 0.0024 (9) | 0.0081 (10) | 0.0040 (9) |
C4 | 0.0179 (12) | 0.0213 (12) | 0.0209 (12) | 0.0019 (9) | 0.0088 (10) | 0.0069 (10) |
C41 | 0.0161 (12) | 0.0177 (12) | 0.0191 (12) | −0.0009 (9) | 0.0037 (9) | 0.0023 (9) |
C42 | 0.0227 (12) | 0.0192 (12) | 0.0198 (12) | 0.0007 (10) | 0.0053 (10) | 0.0052 (10) |
C43 | 0.0169 (12) | 0.0176 (12) | 0.0232 (13) | 0.0009 (9) | 0.0062 (10) | 0.0029 (10) |
O43 | 0.0307 (9) | 0.0250 (9) | 0.0285 (10) | 0.0113 (7) | 0.0126 (8) | 0.0062 (7) |
C431 | 0.0385 (15) | 0.0282 (14) | 0.0254 (14) | 0.0076 (12) | 0.0139 (12) | 0.0017 (11) |
C44 | 0.0209 (12) | 0.0152 (12) | 0.0242 (13) | 0.0024 (9) | 0.0020 (10) | 0.0068 (10) |
O44 | 0.0234 (9) | 0.0218 (9) | 0.0284 (9) | 0.0038 (7) | 0.0012 (7) | 0.0101 (7) |
C441 | 0.0306 (15) | 0.0326 (15) | 0.0332 (15) | 0.0022 (12) | −0.0038 (12) | 0.0071 (12) |
C45 | 0.0254 (13) | 0.0228 (12) | 0.0184 (12) | 0.0001 (10) | 0.0060 (10) | 0.0073 (10) |
O45 | 0.0363 (10) | 0.0372 (10) | 0.0240 (9) | 0.0114 (8) | 0.0116 (8) | 0.0137 (8) |
C451 | 0.0428 (16) | 0.0449 (16) | 0.0244 (14) | 0.0102 (13) | 0.0179 (12) | 0.0090 (12) |
C46 | 0.0216 (12) | 0.0198 (12) | 0.0217 (13) | 0.0040 (10) | 0.0087 (10) | 0.0038 (10) |
C5 | 0.0188 (12) | 0.0214 (12) | 0.0201 (12) | 0.0021 (10) | 0.0080 (10) | 0.0043 (10) |
C51 | 0.0224 (13) | 0.0166 (12) | 0.0247 (13) | 0.0034 (10) | 0.0064 (11) | 0.0046 (10) |
N51 | 0.0335 (12) | 0.0266 (11) | 0.0277 (12) | 0.0033 (10) | 0.0038 (10) | 0.0040 (9) |
C6 | 0.0201 (12) | 0.0188 (12) | 0.0203 (12) | 0.0009 (10) | 0.0081 (10) | 0.0023 (10) |
C61 | 0.0224 (13) | 0.0210 (12) | 0.0183 (12) | 0.0039 (10) | 0.0055 (10) | 0.0036 (9) |
C62 | 0.0248 (13) | 0.0206 (13) | 0.0246 (13) | 0.0048 (10) | 0.0065 (11) | 0.0059 (10) |
N63 | 0.0240 (11) | 0.0200 (11) | 0.0326 (12) | −0.0007 (9) | 0.0044 (9) | 0.0012 (9) |
C63A | 0.0232 (13) | 0.0207 (13) | 0.0281 (14) | 0.0035 (10) | 0.0069 (11) | 0.0036 (10) |
C64 | 0.0303 (15) | 0.0195 (13) | 0.0422 (16) | 0.0012 (11) | 0.0065 (12) | 0.0002 (11) |
C65 | 0.0334 (16) | 0.0269 (14) | 0.0401 (16) | 0.0112 (12) | 0.0074 (12) | 0.0027 (12) |
C66 | 0.0216 (13) | 0.0317 (15) | 0.0310 (14) | 0.0064 (11) | 0.0039 (11) | 0.0050 (11) |
C67 | 0.0266 (14) | 0.0216 (13) | 0.0226 (13) | 0.0023 (10) | 0.0045 (10) | 0.0039 (10) |
C67A | 0.0226 (13) | 0.0219 (12) | 0.0191 (12) | 0.0030 (10) | 0.0048 (10) | 0.0058 (10) |
N7 | 0.0212 (10) | 0.0200 (10) | 0.0209 (10) | 0.0011 (8) | 0.0068 (8) | 0.0038 (8) |
C7A | 0.0175 (12) | 0.0213 (12) | 0.0193 (12) | 0.0016 (9) | 0.0079 (10) | 0.0024 (10) |
Geometric parameters (Å, º) top
N1—C7A | 1.363 (3) | C44—C45 | 1.394 (3) |
N1—N2 | 1.382 (2) | O44—C441 | 1.446 (3) |
N1—C11 | 1.427 (3) | C441—H44A | 0.98 |
C11—C16 | 1.383 (3) | C441—H44B | 0.98 |
C11—C12 | 1.385 (3) | C441—H44C | 0.98 |
C12—C13 | 1.389 (3) | C45—O45 | 1.368 (3) |
C12—H12 | 0.95 | C45—C46 | 1.387 (3) |
C13—C14 | 1.383 (3) | O45—C451 | 1.432 (3) |
C13—H13 | 0.95 | C451—H45A | 0.98 |
C14—C15 | 1.389 (3) | C451—H45B | 0.98 |
C14—H14 | 0.95 | C451—H45C | 0.98 |
C15—C16 | 1.382 (3) | C46—H46 | 0.95 |
C15—H15 | 0.95 | C5—C6 | 1.431 (3) |
C16—H16 | 0.95 | C5—C51 | 1.441 (3) |
N2—C3 | 1.322 (3) | C51—N51 | 1.151 (3) |
C3—C3A | 1.436 (3) | C6—N7 | 1.340 (3) |
C3—C31 | 1.496 (3) | C6—C61 | 1.458 (3) |
C31—H31A | 0.98 | C61—C62 | 1.375 (3) |
C31—H31B | 0.98 | C61—C67A | 1.446 (3) |
C31—H31C | 0.98 | C62—N63 | 1.359 (3) |
C3A—C4 | 1.399 (3) | C62—H62 | 0.95 |
C3A—C7A | 1.409 (3) | N63—C63A | 1.384 (3) |
C4—C5 | 1.404 (3) | N63—H63 | 0.88 |
C4—C41 | 1.485 (3) | C63A—C64 | 1.386 (3) |
C41—C42 | 1.388 (3) | C63A—C67A | 1.411 (3) |
C41—C46 | 1.391 (3) | C64—C65 | 1.377 (4) |
C42—C43 | 1.388 (3) | C64—H64 | 0.95 |
C42—H42 | 0.95 | C65—C66 | 1.398 (3) |
C43—O43 | 1.363 (3) | C65—H65 | 0.95 |
C43—C44 | 1.393 (3) | C66—C67 | 1.375 (3) |
O43—C431 | 1.432 (3) | C66—H66 | 0.95 |
C431—H43A | 0.98 | C67—C67A | 1.401 (3) |
C431—H43B | 0.98 | C67—H67 | 0.95 |
C431—H43C | 0.98 | N7—C7A | 1.345 (3) |
C44—O44 | 1.383 (2) | | |
| | | |
C7A—N1—N2 | 110.62 (17) | O44—C441—H44A | 109.5 |
C7A—N1—C11 | 129.55 (18) | O44—C441—H44B | 109.5 |
N2—N1—C11 | 119.71 (17) | H44A—C441—H44B | 109.5 |
C16—C11—C12 | 120.7 (2) | O44—C441—H44C | 109.5 |
C16—C11—N1 | 120.2 (2) | H44A—C441—H44C | 109.5 |
C12—C11—N1 | 119.09 (19) | H44B—C441—H44C | 109.5 |
C11—C12—C13 | 119.5 (2) | O45—C45—C46 | 124.4 (2) |
C11—C12—H12 | 120.2 | O45—C45—C44 | 115.25 (19) |
C13—C12—H12 | 120.2 | C46—C45—C44 | 120.3 (2) |
C14—C13—C12 | 120.2 (2) | C45—O45—C451 | 117.26 (18) |
C14—C13—H13 | 119.9 | O45—C451—H45A | 109.5 |
C12—C13—H13 | 119.9 | O45—C451—H45B | 109.5 |
C13—C14—C15 | 119.7 (2) | H45A—C451—H45B | 109.5 |
C13—C14—H14 | 120.2 | O45—C451—H45C | 109.5 |
C15—C14—H14 | 120.2 | H45A—C451—H45C | 109.5 |
C16—C15—C14 | 120.5 (2) | H45B—C451—H45C | 109.5 |
C16—C15—H15 | 119.7 | C45—C46—C41 | 119.3 (2) |
C14—C15—H15 | 119.7 | C45—C46—H46 | 120.4 |
C15—C16—C11 | 119.4 (2) | C41—C46—H46 | 120.4 |
C15—C16—H16 | 120.3 | C4—C5—C6 | 122.00 (19) |
C11—C16—H16 | 120.3 | C4—C5—C51 | 119.73 (19) |
C3—N2—N1 | 107.10 (17) | C6—C5—C51 | 118.24 (19) |
N2—C3—C3A | 110.48 (19) | N51—C51—C5 | 177.7 (2) |
N2—C3—C31 | 119.2 (2) | N7—C6—C5 | 122.14 (19) |
C3A—C3—C31 | 130.3 (2) | N7—C6—C61 | 116.84 (19) |
C3—C31—H31A | 109.5 | C5—C6—C61 | 121.03 (19) |
C3—C31—H31B | 109.5 | C62—C61—C67A | 106.24 (19) |
H31A—C31—H31B | 109.5 | C62—C61—C6 | 127.1 (2) |
C3—C31—H31C | 109.5 | C67A—C61—C6 | 126.6 (2) |
H31A—C31—H31C | 109.5 | N63—C62—C61 | 110.3 (2) |
H31B—C31—H31C | 109.5 | N63—C62—H62 | 124.8 |
C4—C3A—C7A | 118.15 (19) | C61—C62—H62 | 124.8 |
C4—C3A—C3 | 137.1 (2) | C62—N63—C63A | 109.21 (19) |
C7A—C3A—C3 | 104.59 (18) | C62—N63—H63 | 125.4 |
C3A—C4—C5 | 115.42 (19) | C63A—N63—H63 | 125.4 |
C3A—C4—C41 | 122.83 (19) | N63—C63A—C64 | 130.2 (2) |
C5—C4—C41 | 121.75 (19) | N63—C63A—C67A | 107.50 (19) |
C42—C41—C46 | 120.9 (2) | C64—C63A—C67A | 122.3 (2) |
C42—C41—C4 | 119.0 (2) | C65—C64—C63A | 117.6 (2) |
C46—C41—C4 | 120.06 (19) | C65—C64—H64 | 121.2 |
C41—C42—C43 | 119.6 (2) | C63A—C64—H64 | 121.2 |
C41—C42—H42 | 120.2 | C64—C65—C66 | 121.1 (2) |
C43—C42—H42 | 120.2 | C64—C65—H65 | 119.5 |
O43—C43—C42 | 124.6 (2) | C66—C65—H65 | 119.5 |
O43—C43—C44 | 115.29 (19) | C67—C66—C65 | 121.5 (2) |
C42—C43—C44 | 120.1 (2) | C67—C66—H66 | 119.2 |
C43—O43—C431 | 117.41 (17) | C65—C66—H66 | 119.2 |
O43—C431—H43A | 109.5 | C66—C67—C67A | 118.6 (2) |
O43—C431—H43B | 109.5 | C66—C67—H67 | 120.7 |
H43A—C431—H43B | 109.5 | C67A—C67—H67 | 120.7 |
O43—C431—H43C | 109.5 | C67—C67A—C63A | 118.8 (2) |
H43A—C431—H43C | 109.5 | C67—C67A—C61 | 134.3 (2) |
H43B—C431—H43C | 109.5 | C63A—C67A—C61 | 106.71 (19) |
O44—C44—C43 | 118.7 (2) | C6—N7—C7A | 114.83 (18) |
O44—C44—C45 | 121.3 (2) | N7—C7A—N1 | 125.50 (19) |
C43—C44—C45 | 119.81 (19) | N7—C7A—C3A | 127.3 (2) |
C44—O44—C441 | 115.08 (17) | N1—C7A—C3A | 107.19 (18) |
| | | |
C7A—N1—C11—C16 | 37.4 (3) | C44—C45—C46—C41 | −0.9 (3) |
N2—N1—C11—C16 | −147.0 (2) | C42—C41—C46—C45 | −0.8 (3) |
C7A—N1—C11—C12 | −141.2 (2) | C4—C41—C46—C45 | 178.3 (2) |
N2—N1—C11—C12 | 34.4 (3) | C3A—C4—C5—C6 | 2.7 (3) |
C16—C11—C12—C13 | −2.6 (4) | C41—C4—C5—C6 | −178.1 (2) |
N1—C11—C12—C13 | 176.0 (2) | C3A—C4—C5—C51 | −175.1 (2) |
C11—C12—C13—C14 | 1.0 (4) | C41—C4—C5—C51 | 4.1 (3) |
C12—C13—C14—C15 | 1.2 (4) | C4—C5—C6—N7 | −4.2 (3) |
C13—C14—C15—C16 | −2.0 (4) | C51—C5—C6—N7 | 173.7 (2) |
C14—C15—C16—C11 | 0.4 (4) | C4—C5—C6—C61 | 176.0 (2) |
C12—C11—C16—C15 | 1.9 (3) | C51—C5—C6—C61 | −6.2 (3) |
N1—C11—C16—C15 | −176.7 (2) | N7—C6—C61—C62 | 134.9 (2) |
C7A—N1—N2—C3 | −0.6 (2) | C5—C6—C61—C62 | −45.3 (3) |
C11—N1—N2—C3 | −176.94 (19) | N7—C6—C61—C67A | −44.7 (3) |
N1—N2—C3—C3A | 1.1 (2) | C5—C6—C61—C67A | 135.2 (2) |
N1—N2—C3—C31 | −176.4 (2) | C67A—C61—C62—N63 | 1.0 (3) |
N2—C3—C3A—C4 | −175.8 (3) | C6—C61—C62—N63 | −178.6 (2) |
C31—C3—C3A—C4 | 1.4 (5) | C61—C62—N63—C63A | −1.0 (3) |
N2—C3—C3A—C7A | −1.2 (3) | C62—N63—C63A—C64 | −177.2 (2) |
C31—C3—C3A—C7A | 175.9 (2) | C62—N63—C63A—C67A | 0.6 (3) |
C7A—C3A—C4—C5 | 0.7 (3) | N63—C63A—C64—C65 | 176.3 (2) |
C3—C3A—C4—C5 | 174.7 (2) | C67A—C63A—C64—C65 | −1.1 (4) |
C7A—C3A—C4—C41 | −178.5 (2) | C63A—C64—C65—C66 | −1.1 (4) |
C3—C3A—C4—C41 | −4.5 (4) | C64—C65—C66—C67 | 2.0 (4) |
C3A—C4—C41—C42 | −56.7 (3) | C65—C66—C67—C67A | −0.6 (4) |
C5—C4—C41—C42 | 124.1 (2) | C66—C67—C67A—C63A | −1.6 (3) |
C3A—C4—C41—C46 | 124.2 (2) | C66—C67—C67A—C61 | −175.6 (2) |
C5—C4—C41—C46 | −55.0 (3) | N63—C63A—C67A—C67 | −175.4 (2) |
C46—C41—C42—C43 | 0.6 (3) | C64—C63A—C67A—C67 | 2.5 (4) |
C4—C41—C42—C43 | −178.5 (2) | N63—C63A—C67A—C61 | 0.1 (3) |
C41—C42—C43—O43 | −178.99 (19) | C64—C63A—C67A—C61 | 178.0 (2) |
C41—C42—C43—C44 | 1.3 (3) | C62—C61—C67A—C67 | 173.9 (2) |
C42—C43—O43—C431 | 9.0 (3) | C6—C61—C67A—C67 | −6.5 (4) |
C44—C43—O43—C431 | −171.3 (2) | C62—C61—C67A—C63A | −0.6 (2) |
O43—C43—C44—O44 | 2.7 (3) | C6—C61—C67A—C63A | 179.0 (2) |
C42—C43—C44—O44 | −177.58 (19) | C5—C6—N7—C7A | 1.7 (3) |
O43—C43—C44—C45 | 177.25 (19) | C61—C6—N7—C7A | −178.42 (19) |
C42—C43—C44—C45 | −3.0 (3) | C6—N7—C7A—N1 | −177.9 (2) |
C43—C44—O44—C441 | −119.0 (2) | C6—N7—C7A—C3A | 2.0 (3) |
C45—C44—O44—C441 | 66.5 (3) | N2—N1—C7A—N7 | 179.7 (2) |
O44—C44—C45—O45 | −1.3 (3) | C11—N1—C7A—N7 | −4.4 (4) |
C43—C44—C45—O45 | −175.67 (19) | N2—N1—C7A—C3A | −0.2 (2) |
O44—C44—C45—C46 | 177.23 (19) | C11—N1—C7A—C3A | 175.7 (2) |
C43—C44—C45—C46 | 2.8 (3) | C4—C3A—C7A—N7 | −3.3 (3) |
C46—C45—O45—C451 | −9.7 (3) | C3—C3A—C7A—N7 | −179.1 (2) |
C44—C45—O45—C451 | 168.7 (2) | C4—C3A—C7A—N1 | 176.6 (2) |
O45—C45—C46—C41 | 177.4 (2) | C3—C3A—C7A—N1 | 0.8 (2) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N63—H63···O44i | 0.88 | 2.06 | 2.938 (2) | 173 |
Symmetry code: (i) x, y−1, z. |
Experimental details
| (I) | (II) | (III) |
Crystal data |
Chemical formula | C29H21N5·C3H7NO | C29H21N5O·C3H7NO | C31H25N5O3 |
Mr | 512.60 | 528.60 | 515.56 |
Crystal system, space group | Triclinic, P1 | Monoclinic, C2/c | Triclinic, P1 |
Temperature (K) | 120 | 120 | 120 |
a, b, c (Å) | 9.8060 (3), 10.1820 (3), 13.818 (2) | 30.303 (3), 11.3490 (16), 20.344 (3) | 8.8241 (10), 11.9901 (9), 12.9130 (17) |
α, β, γ (°) | 97.035 (6), 104.455 (6), 96.171 (3) | 90, 131.010 (5), 90 | 99.372 (9), 108.822 (12), 90.994 (7) |
V (Å3) | 1312.2 (2) | 5279.5 (12) | 1272.3 (3) |
Z | 2 | 8 | 2 |
Radiation type | Mo Kα | Mo Kα | Mo Kα |
µ (mm−1) | 0.08 | 0.09 | 0.09 |
Crystal size (mm) | 0.40 × 0.18 × 0.18 | 0.51 × 0.49 × 0.27 | 0.38 × 0.20 × 0.18 |
|
Data collection |
Diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer | Bruker–Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.961, 0.985 | 0.949, 0.977 | 0.960, 0.984 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 31081, 5996, 3816 | 63662, 6055, 3416 | 31225, 5825, 3165 |
Rint | 0.048 | 0.074 | 0.075 |
(sin θ/λ)max (Å−1) | 0.650 | 0.650 | 0.649 |
|
Refinement |
R[F2 > 2σ(F2)], wR(F2), S | 0.050, 0.146, 1.06 | 0.069, 0.237, 1.07 | 0.055, 0.152, 1.06 |
No. of reflections | 5996 | 6055 | 5825 |
No. of parameters | 356 | 365 | 356 |
H-atom treatment | H-atom parameters constrained | H-atom parameters constrained | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.37, −0.31 | 0.43, −0.34 | 0.27, −0.35 |
Selected torsion angles and bond angles (°) for
compounds (I)–(III) topParameter | (I) | (II) | (III) |
N2—N1—C11—C12 | 9.5 (3) | 13.1 (4) | 34.4 (3) |
C3A—C4—C41—C42 | 57.4 (3) | 61.4 (4) | -56.7 (3) |
C5—C6—C61—C62 | 29.3 (3) | 28.6 (4) | -45.3 (3) |
C42—C43—O43—C431 | | | 9.0 (3) |
C43—C44—O44—C441 | | -172.3 (2) | -119.0 (2) |
C46—C45—O45—C451 | | | -9.7 (3) |
C42—C43—O43 | | | 124.6 (2) |
C44—C43—O43 | | | 115.29 (19) |
C43—C44—O44 | | 116.0 (2) | 118.7 (2) |
C45—C44—O44 | | 124.3 (3) | 121.3 (2) |
C44—C45—O45 | | | 115.25 (19) |
C46—-C45—O45 | | | 124.4 (2) |
C43—O43—C431 | | | 117.41 (17) |
C44—O44—C441 | | 116.3 (2) | 115.08 (17) |
C45—O45—C451 | | | 117.26 (18) |
Hydrogen bond parameters (Å, °) for compounds (I) - (III) topCompound | D—H···A | D—H | H···A | D···A | D—H···A |
(I) | N63—H63···O20 | 0.88 | 1.89 | 2.767 (2) | 173 |
| C42—H42···Cgi | 0.95 | 2.65 | 3.514 (3) | 151 |
(II) | N63—H63···O20 | 0.88 | 1.96 | 2.757 (5) | 149 |
| C42—H42···Cgii | 0.95 | 2.68 | 3.558 (3) | 154 |
| C46—H46···N51iii | 0.95 | 2.43 | 3.213 (4) | 140 |
(III) | N63—H63···O44iv | 0.88 | 2.06 | 2.939 (2) | 173 |
Symmetry codes: (i) -x + 1, -y + 1, -z + 1; (ii)
-x + 1/2, -y + 3/2, -z + 1; (iii) -x = 1/2, -y + 1/2, -z + 1;
(iv) x, -1 + y, z.
Cg represents the centroid of the
ring C63A/C64–C67/C67A. |
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We report here the structures of three 6-(1H-indol-3-yl)-3-methyl-1-phenyl-4-aryl-1H- pyrazolo[3,4-b]pyridine-5-carbonitriles, two of which crystallize from dimethylformamide solutions as stoichiometric monosolvates, namely 6-(1H-indol-3-yl)-3-methyl-1-phenyl-4-(4-methylphenyl)-1H- pyrazolo[3,4-b]pyridine-5-carbonitrile–dimethylformamide (1/1), (I), 6-(1H-indol-3-yl)-3-methyl-1-phenyl-4-(4-methoxyphenyl)-1H- pyrazolo[3,4-b]pyridine-5-carbonitrile–dimethylformamide (1/1), (II), and the solvent-free 6-(1H-indol-3-yl)-3-methyl-1-phenyl- 4-(3,4,5-trimethoxyphenyl)-1H-pyrazolo[3,4-b]pyridine-5-carbonitrile, (III) (Figs. 1–3). The heterocyclic components within this group differ only in the substituents on the pendent aryl ring (C41–C46).
As a part of our exploration of routes to new biologically interesting pyrazolo[3,4-b]pyridine derivatives, we have sought methods for the introduction of an indolyl residue as a substituent at C-6, in order to establish the influence of this naturally occurring group on the biological activity of the resulting products. To this end, we have adapted the multicomponent reaction between substituted aryl aldehydes, an aminopyrazole and a ketone derivative, which has been used for the synthesis of fused heterocyclic systems (Quiroga et al., 2007) to include the use of 3-(2-cyanoacetyl)indole. The corresponding reactions utilizing mixtures of 5-amino-3-methyl-1-phenylpyrazole and 3-(2-cyanoacetyl)indole with three different substituted aryl aldehydes were conducted using microwave irradiation under solvent-free conditions to produce the corresponding 6-(1H-indol-3-yl)-3-methyl-1-phenyl-4-arylpyrazolo[3,4-b]pyridine- 5-carbonitriles, (I)–(III) (Scheme 2).
With the exception of the methoxy groups in compounds (II) and (III), the skeletal conformations of the heterocyclic components can be defined in terms of just three torsion angles, which define the orientation of the three cyclic substituents relative to the central pyrazolopyridine unit (Table 1). In each compound, the rotation of the substituents out of the plane of the pyrazolopyridine unit is least for the C11–C16 aryl ring and most for the C41–C46 aryl ring. Simple steric considerations, particularly those involving the methyl and cyano substituents at atoms C3 and C5, account for this order, although not for the detailed differences in the torsion angles.
The methoxy C atom in compound (II) is almost coplanar with the adjacent aryl ring, as are the methoxy atoms C431 and C451 in compound (III); on the other hand, the C44/O44/C441 plane defining the orientation of the central methoxy substituent in compound (III) is at an angle of almost 60° to the adjacent aryl ring. The exocyclic C—C—O bond angles exhibit the usual pattern, with the two values at each substituent differing by almost 10° for the in-plane methoxy groups, while for the out of plane methoxy group in compound (III), these angles differ by very much less (Table 1).
In each of the solvates (I) and (II), the molecular components within the selected asymmetric units are linked by an N—H···O hydrogen bond (Table 2), so that the N—H bond is not available for the formation of a hydrogen bond to another heterocyclic molecule. In compound (I), the heterocyclic components are linked by a C—H···π(arene) hydrogen bond; atom C42 at (x, y, z) acts as a hydrogen-bond donor to the aryl ring C63A/C64–C67/C67A at (1 - x, 1 - y, 1 - z), so generating by inversion a cyclic centrosymmetric dimer, centred at (1/2, 1/2, 1/2) (Fig. 4), from which two dimethylformamide molecules are pendent.
The aggregation of the pyrazolopyridine components in compound (II) utilizes both C—H···π(arene) and C—H···N hydrogen bonds (Table 2). As in compound (I), atom C42 at (x, y, z) acts as a hydrogen-bond donor to the aryl ring C63A/C64–C67/C67A, now at (1/2 - x, 3/2 - y, 1 - z), so generating by inversion a cyclic centrosymmetric motif. In addition, C46 at (x, y, z) acts as a donor to nitrile atom N51 at (1/2 - x, 1/2 - y, 1 - z), thus generating by inversion a centrosymmetric R22(14) (Bernstein et al., 1995) motif. Propagation by inversion of these two hydrogen bonds then generates a chain of rings parallel to [010], with rings containing pairs of C—H···π(arene) hydrogen bonds centred at (1/4, n - 1/4, 1/2) (where n represents zero or an integer) alternating with rings containing pairs of C—H···N hydrogen bonds centred at (1/4, n + 1/4, 1/2) (where n represents zero or an integer) (Fig. 5). The dimethylformamide solvent molecules are pendent from the chain, linked to it via N—H···O hydrogen bonds. Four chains of this type pass through each unit cell, but there are no direction-specific interactions between the chains.
In the solvent-free compound (III), the molecules are linked by a single, nearly-linear N—H···O hydrogen bond, but C—H···N and C—H···π(arene) hydrogen bonds are absent. Atom N63 in the molecule at (x, y, z) acts as a hydrogen-bond donor to the central methoxy atom O44 in the molecule at (x, -1 + y, z), so generating by translation a C(12) chain running parallel to the [010] direction (Fig. 6).
In each compound, there is a rather weak π–π stacking interaction involving the pyridyl rings in pairs of molecules related by inversion. In compounds (I) and (III), the rings involved are at (x, y, z) and (1 - x, 1 - y, 1 - z), while in compound (II), they are at (x, y, z) and (1/2 - x, 3/2 - y, 1 - z). The interplanar spacings in compounds (I), (II) and (III) are 3.632 (2), 3.538 (2) and 3.583 (2) Å, respectively, and the ring-centroid separations are 3.956 (2), 3.815 (2) and 3.831 (2) Å, corresponding to ring-centroid offsets of 1.568 (2), 1.427 (2) and 1.356 (2) Å, respectively. In compounds (I) and (II), the interactions weakly augment the actions of the C—H···π(arene) hydrogen bonds; in compound (III), the stacking interactions link, albeit weakly, an antiparallel pair of C(12) chains.