Supporting information
Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270109025566/su3034sup1.cif | |
Structure factor file (CIF format) https://doi.org/10.1107/S0108270109025566/su3034Isup2.hkl |
CCDC reference: 746071
An equimolar mixture of 2-fluorobenzaldehyde, 5-amino-3-methyl-1-henylpyrazole [phenyl?] and 3-(2-cyanoacetyl)indole was subjected to microwave irradiation in the absence of solvent, using a focused microwave reaction (CEM Discover), with maximum power 300 W during 9 min at a controlled temperature of 473 K. The reaction mixture was allowed to cool to ambient temperature, and it was then extracted with hot ethanol/dimethylformamide (2:1, v/v); the combined extracts were reduced to small volume and the resulting solid product was collected by filtration, and washed successively with ethanol and diethyl ether to provide colourless crystals of the title compound (I) suitable for single-crystal X-ray diffraction (yield 83%, m.p. 570–571 K). MS (EI, 70 eV) m/z (%) = 443 (100, M+), 350 (44), 140 (11), 77 (43), 51 (30).
All H atoms were located in difference electron-density maps, and then treated as riding atoms in geometrically idealized positions with distances C—H 0.95 Å (aromatic and heteroaromatic), or 0.98 Å (methyl) and N—H 0.88 Å, and with Uiso(H) = kUeq(carrier), where k = 1.5 for the methyl group, which was permitted to rotate but not to tilt, and 1.2 for all other H atoms. Refinement based on the presence only of the pyrazolopyridine molecule converged to R = 0.141, with several unacceptably large peaks in the difference electron-density map. At this point, examination of the refined structure using PLATON (Spek, 2009) indicated the presence of four symmetry-related voids per cell, each of volume ca 104 Å3, located at (0, 0.335, 1/4), (0. 0.665, 3/4), (1/2, 0.835, 1/4) and (1/2, 0.165, 3/4). Within each void, there were four residual peaks in a T-shaped arrangement, with the shaft of the T lying along a twofold rotation axis, and an angle of ca 92° between the shaft and the crosspieces of the T: no plausible solvent model, for example based upon two partially occupied methanol sites, could be developed from these peaks, hence the SQUEEZE option in PLATON was applied, which indicated 7 electrons per void, and which led to an acceptable R factor, with satisfactory values for the electron-density residuals.
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: SHELXS97 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: PLATON (Spek, 2009); software used to prepare material for publication: SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
C28H18FN5 | F(000) = 1840 |
Mr = 443.47 | Dx = 1.280 Mg m−3 |
Monoclinic, C2/c | Mo Kα radiation, λ = 0.71073 Å |
Hall symbol: -C 2yc | Cell parameters from 5280 reflections |
a = 24.155 (3) Å | θ = 3.2–27.5° |
b = 10.5830 (7) Å | µ = 0.08 mm−1 |
c = 18.712 (3) Å | T = 120 K |
β = 105.743 (10)° | Block, colourless |
V = 4604.0 (10) Å3 | 0.45 × 0.26 × 0.25 mm |
Z = 8 |
Bruker Nonius KappaCCD diffractometer | 5280 independent reflections |
Radiation source: Bruker-Nonius FR591 rotating anode | 3346 reflections with I > 2σ(I) |
Graphite monochromator | Rint = 0.065 |
Detector resolution: 9.091 pixels mm-1 | θmax = 27.5°, θmin = 3.2° |
ϕ & ω scans | h = −31→31 |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | k = −13→13 |
Tmin = 0.968, Tmax = 0.979 | l = −24→24 |
51259 measured reflections |
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) = 0.211 | H-atom parameters constrained |
S = 1.10 | w = 1/[σ2(Fo2) + (0.1279P)2] where P = (Fo2 + 2Fc2)/3 |
5280 reflections | (Δ/σ)max = 0.001 |
308 parameters | Δρmax = 0.38 e Å−3 |
0 restraints | Δρmin = −0.29 e Å−3 |
C28H18FN5 | V = 4604.0 (10) Å3 |
Mr = 443.47 | Z = 8 |
Monoclinic, C2/c | Mo Kα radiation |
a = 24.155 (3) Å | µ = 0.08 mm−1 |
b = 10.5830 (7) Å | T = 120 K |
c = 18.712 (3) Å | 0.45 × 0.26 × 0.25 mm |
β = 105.743 (10)° |
Bruker Nonius KappaCCD diffractometer | 5280 independent reflections |
Absorption correction: multi-scan (SADABS; Sheldrick, 2003) | 3346 reflections with I > 2σ(I) |
Tmin = 0.968, Tmax = 0.979 | Rint = 0.065 |
51259 measured reflections |
R[F2 > 2σ(F2)] = 0.069 | 0 restraints |
wR(F2) = 0.211 | H-atom parameters constrained |
S = 1.10 | Δρmax = 0.38 e Å−3 |
5280 reflections | Δρmin = −0.29 e Å−3 |
308 parameters |
x | y | z | Uiso*/Ueq | ||
N1 | 0.23023 (8) | 0.05625 (16) | 0.59693 (11) | 0.0260 (4) | |
N2 | 0.25698 (8) | −0.04293 (18) | 0.57125 (11) | 0.0284 (5) | |
C3 | 0.30434 (10) | 0.0025 (2) | 0.55817 (13) | 0.0266 (5) | |
C3A | 0.30961 (9) | 0.1348 (2) | 0.57526 (12) | 0.0252 (5) | |
C4 | 0.35003 (9) | 0.2307 (2) | 0.57830 (12) | 0.0248 (5) | |
C5 | 0.33732 (9) | 0.3477 (2) | 0.60517 (12) | 0.0251 (5) | |
C6 | 0.28349 (9) | 0.3700 (2) | 0.62212 (12) | 0.0255 (5) | |
N7 | 0.24613 (8) | 0.27690 (16) | 0.62049 (10) | 0.0253 (4) | |
C7A | 0.26120 (9) | 0.1643 (2) | 0.60033 (12) | 0.0247 (5) | |
C11 | 0.17574 (9) | 0.0383 (2) | 0.61160 (13) | 0.0262 (5) | |
C12 | 0.16577 (10) | 0.0889 (2) | 0.67510 (13) | 0.0304 (5) | |
H12 | 0.1954 | 0.1331 | 0.7099 | 0.036* | |
C13 | 0.11224 (11) | 0.0744 (2) | 0.68726 (15) | 0.0379 (6) | |
H13 | 0.1050 | 0.1081 | 0.7309 | 0.046* | |
C14 | 0.06897 (11) | 0.0106 (3) | 0.63568 (16) | 0.0424 (7) | |
H14 | 0.0320 | 0.0023 | 0.6437 | 0.051* | |
C15 | 0.07947 (11) | −0.0404 (3) | 0.57333 (16) | 0.0409 (7) | |
H15 | 0.0498 | −0.0847 | 0.5386 | 0.049* | |
C16 | 0.13338 (10) | −0.0275 (2) | 0.56082 (13) | 0.0313 (6) | |
H16 | 0.1410 | −0.0634 | 0.5179 | 0.038* | |
C31 | 0.34417 (10) | −0.0832 (2) | 0.53262 (14) | 0.0334 (6) | |
H31A | 0.3296 | −0.1700 | 0.5299 | 0.050* | |
H31B | 0.3825 | −0.0794 | 0.5678 | 0.050* | |
H31C | 0.3466 | −0.0565 | 0.4834 | 0.050* | |
C41 | 0.40241 (10) | 0.2080 (2) | 0.55290 (13) | 0.0278 (5) | |
C42 | 0.45715 (10) | 0.2061 (2) | 0.60056 (14) | 0.0320 (6) | |
F42 | 0.46346 (6) | 0.22698 (15) | 0.67355 (8) | 0.0459 (4) | |
C43 | 0.50512 (11) | 0.1817 (2) | 0.57729 (16) | 0.0402 (6) | |
H43 | 0.5421 | 0.1792 | 0.6118 | 0.048* | |
C44 | 0.49875 (11) | 0.1608 (2) | 0.50246 (16) | 0.0407 (7) | |
H44 | 0.5316 | 0.1451 | 0.4852 | 0.049* | |
C45 | 0.44480 (10) | 0.1627 (2) | 0.45284 (15) | 0.0367 (6) | |
H45 | 0.4407 | 0.1487 | 0.4015 | 0.044* | |
C46 | 0.39693 (10) | 0.1848 (2) | 0.47759 (13) | 0.0307 (6) | |
H46 | 0.3598 | 0.1843 | 0.4433 | 0.037* | |
C51 | 0.38009 (10) | 0.4463 (2) | 0.61782 (13) | 0.0297 (5) | |
N51 | 0.41494 (9) | 0.5227 (2) | 0.62936 (12) | 0.0372 (5) | |
N61 | 0.24804 (8) | 0.70441 (18) | 0.63413 (11) | 0.0323 (5) | |
H61 | 0.2510 | 0.7853 | 0.6249 | 0.039* | |
C62 | 0.27979 (10) | 0.6102 (2) | 0.61538 (13) | 0.0295 (5) | |
H62 | 0.3084 | 0.6223 | 0.5898 | 0.035* | |
C63 | 0.26477 (9) | 0.4950 (2) | 0.63852 (13) | 0.0252 (5) | |
C63A | 0.21983 (9) | 0.5210 (2) | 0.67422 (12) | 0.0267 (5) | |
C64 | 0.18794 (10) | 0.4470 (2) | 0.71095 (13) | 0.0298 (5) | |
H64 | 0.1935 | 0.3581 | 0.7152 | 0.036* | |
C65 | 0.14832 (10) | 0.5058 (2) | 0.74078 (13) | 0.0331 (6) | |
H65 | 0.1268 | 0.4565 | 0.7662 | 0.040* | |
C66 | 0.13909 (10) | 0.6368 (2) | 0.73442 (13) | 0.0337 (6) | |
H66 | 0.1108 | 0.6740 | 0.7545 | 0.040* | |
C67 | 0.17025 (10) | 0.7122 (2) | 0.69965 (13) | 0.0326 (6) | |
H67 | 0.1646 | 0.8011 | 0.6960 | 0.039* | |
C67A | 0.21044 (10) | 0.6523 (2) | 0.67000 (12) | 0.0274 (5) |
U11 | U22 | U33 | U12 | U13 | U23 | |
N1 | 0.0259 (10) | 0.0202 (10) | 0.0327 (11) | −0.0005 (8) | 0.0094 (8) | −0.0027 (8) |
N2 | 0.0283 (11) | 0.0263 (10) | 0.0321 (11) | 0.0004 (8) | 0.0106 (8) | −0.0027 (8) |
C3 | 0.0254 (12) | 0.0288 (12) | 0.0257 (12) | 0.0018 (10) | 0.0070 (9) | 0.0031 (9) |
C3A | 0.0232 (11) | 0.0267 (12) | 0.0248 (12) | 0.0003 (9) | 0.0050 (9) | 0.0025 (9) |
C4 | 0.0223 (11) | 0.0275 (12) | 0.0246 (11) | 0.0021 (9) | 0.0067 (9) | 0.0025 (9) |
C5 | 0.0237 (11) | 0.0263 (12) | 0.0260 (12) | −0.0032 (9) | 0.0079 (9) | 0.0019 (9) |
C6 | 0.0230 (11) | 0.0296 (12) | 0.0238 (12) | −0.0015 (9) | 0.0060 (9) | 0.0031 (9) |
N7 | 0.0245 (10) | 0.0235 (10) | 0.0281 (10) | −0.0005 (8) | 0.0074 (8) | 0.0008 (8) |
C7A | 0.0236 (11) | 0.0254 (12) | 0.0255 (12) | 0.0002 (9) | 0.0072 (9) | 0.0021 (9) |
C11 | 0.0211 (11) | 0.0263 (12) | 0.0323 (12) | 0.0016 (9) | 0.0091 (9) | 0.0051 (10) |
C12 | 0.0292 (12) | 0.0294 (13) | 0.0315 (13) | 0.0009 (10) | 0.0064 (10) | 0.0021 (10) |
C13 | 0.0351 (14) | 0.0426 (15) | 0.0422 (15) | 0.0013 (11) | 0.0210 (12) | 0.0039 (12) |
C14 | 0.0273 (13) | 0.0467 (16) | 0.0566 (18) | −0.0016 (12) | 0.0173 (13) | 0.0084 (13) |
C15 | 0.0289 (13) | 0.0397 (15) | 0.0511 (16) | −0.0079 (11) | 0.0057 (12) | 0.0027 (13) |
C16 | 0.0302 (13) | 0.0304 (13) | 0.0325 (13) | −0.0046 (10) | 0.0071 (10) | 0.0011 (10) |
C31 | 0.0336 (13) | 0.0286 (13) | 0.0396 (14) | 0.0017 (10) | 0.0127 (11) | −0.0021 (11) |
C41 | 0.0246 (12) | 0.0266 (12) | 0.0340 (13) | −0.0009 (9) | 0.0109 (10) | 0.0026 (10) |
C42 | 0.0299 (13) | 0.0342 (14) | 0.0318 (13) | −0.0019 (10) | 0.0081 (10) | 0.0000 (10) |
F42 | 0.0350 (8) | 0.0667 (11) | 0.0320 (8) | −0.0009 (7) | 0.0021 (7) | −0.0013 (7) |
C43 | 0.0250 (13) | 0.0389 (15) | 0.0547 (17) | −0.0003 (11) | 0.0075 (12) | 0.0044 (13) |
C44 | 0.0338 (14) | 0.0361 (15) | 0.0583 (18) | 0.0021 (11) | 0.0231 (13) | −0.0025 (12) |
C45 | 0.0361 (14) | 0.0395 (15) | 0.0379 (14) | 0.0009 (11) | 0.0160 (12) | −0.0004 (12) |
C46 | 0.0302 (13) | 0.0303 (13) | 0.0334 (13) | 0.0013 (10) | 0.0119 (11) | 0.0001 (10) |
C51 | 0.0290 (13) | 0.0300 (13) | 0.0306 (13) | −0.0007 (11) | 0.0086 (10) | 0.0002 (10) |
N51 | 0.0300 (11) | 0.0373 (12) | 0.0453 (13) | −0.0072 (10) | 0.0119 (10) | −0.0042 (10) |
N61 | 0.0338 (11) | 0.0251 (10) | 0.0392 (12) | −0.0016 (8) | 0.0121 (9) | 0.0004 (9) |
C62 | 0.0289 (12) | 0.0280 (12) | 0.0344 (13) | −0.0003 (10) | 0.0131 (10) | −0.0003 (10) |
C63 | 0.0252 (12) | 0.0227 (11) | 0.0284 (12) | −0.0006 (9) | 0.0083 (10) | 0.0000 (9) |
C63A | 0.0235 (12) | 0.0316 (13) | 0.0238 (11) | 0.0009 (9) | 0.0045 (9) | −0.0016 (10) |
C64 | 0.0320 (13) | 0.0283 (13) | 0.0304 (12) | −0.0015 (10) | 0.0104 (10) | −0.0020 (10) |
C65 | 0.0291 (13) | 0.0420 (15) | 0.0297 (13) | −0.0025 (11) | 0.0107 (10) | −0.0012 (11) |
C66 | 0.0306 (13) | 0.0412 (15) | 0.0300 (13) | 0.0037 (11) | 0.0094 (10) | −0.0060 (11) |
C67 | 0.0319 (13) | 0.0338 (14) | 0.0284 (13) | 0.0062 (10) | 0.0018 (10) | −0.0056 (10) |
C67A | 0.0302 (12) | 0.0270 (12) | 0.0250 (12) | 0.0005 (10) | 0.0077 (10) | −0.0012 (9) |
N1—C7A | 1.358 (3) | C41—C42 | 1.380 (3) |
N1—N2 | 1.385 (2) | C41—C46 | 1.401 (3) |
N1—C11 | 1.428 (3) | C42—F42 | 1.351 (3) |
N2—C3 | 1.323 (3) | C42—C43 | 1.368 (3) |
C3—C3A | 1.435 (3) | C43—C44 | 1.384 (4) |
C3—C31 | 1.492 (3) | C43—H43 | 0.9500 |
C3A—C4 | 1.399 (3) | C44—C45 | 1.380 (4) |
C3A—C7A | 1.408 (3) | C44—H44 | 0.9500 |
C4—C5 | 1.401 (3) | C45—C46 | 1.377 (3) |
C4—C41 | 1.487 (3) | C45—H45 | 0.9500 |
C5—C6 | 1.439 (3) | C46—H46 | 0.9500 |
C5—C51 | 1.442 (3) | C51—N51 | 1.145 (3) |
C6—N7 | 1.331 (3) | N61—C62 | 1.361 (3) |
C6—C63 | 1.457 (3) | N61—C67A | 1.382 (3) |
N7—C7A | 1.330 (3) | N61—H61 | 0.8800 |
C11—C16 | 1.381 (3) | C62—C63 | 1.375 (3) |
C11—C12 | 1.383 (3) | C62—H62 | 0.9500 |
C12—C13 | 1.381 (3) | C63—C63A | 1.447 (3) |
C12—H12 | 0.9500 | C63A—C64 | 1.402 (3) |
C13—C14 | 1.390 (4) | C63A—C67A | 1.406 (3) |
C13—H13 | 0.9500 | C64—C65 | 1.380 (3) |
C14—C15 | 1.370 (4) | C64—H64 | 0.9500 |
C14—H14 | 0.9500 | C65—C66 | 1.404 (3) |
C15—C16 | 1.391 (3) | C65—H65 | 0.9500 |
C15—H15 | 0.9500 | C66—C67 | 1.376 (3) |
C16—H16 | 0.9500 | C66—H66 | 0.9500 |
C31—H31A | 0.9800 | C67—C67A | 1.395 (3) |
C31—H31B | 0.9800 | C67—H67 | 0.9500 |
C31—H31C | 0.9800 | ||
C7A—N1—N2 | 110.56 (18) | C42—C41—C46 | 117.4 (2) |
C7A—N1—C11 | 128.88 (18) | C42—C41—C4 | 123.0 (2) |
N2—N1—C11 | 120.44 (17) | C46—C41—C4 | 119.6 (2) |
C3—N2—N1 | 107.28 (18) | F42—C42—C43 | 118.7 (2) |
N2—C3—C3A | 110.01 (19) | F42—C42—C41 | 118.5 (2) |
N2—C3—C31 | 120.2 (2) | C43—C42—C41 | 122.9 (2) |
C3A—C3—C31 | 129.7 (2) | C42—C43—C44 | 118.7 (2) |
C4—C3A—C7A | 117.4 (2) | C42—C43—H43 | 120.6 |
C4—C3A—C3 | 137.4 (2) | C44—C43—H43 | 120.6 |
C7A—C3A—C3 | 105.01 (19) | C45—C44—C43 | 120.2 (2) |
C3A—C4—C5 | 115.92 (19) | C45—C44—H44 | 119.9 |
C3A—C4—C41 | 121.0 (2) | C43—C44—H44 | 119.9 |
C5—C4—C41 | 123.08 (19) | C46—C45—C44 | 120.1 (2) |
C4—C5—C6 | 121.55 (19) | C46—C45—H45 | 119.9 |
C4—C5—C51 | 118.8 (2) | C44—C45—H45 | 119.9 |
C6—C5—C51 | 119.6 (2) | C45—C46—C41 | 120.6 (2) |
N7—C6—C5 | 121.4 (2) | C45—C46—H46 | 119.7 |
N7—C6—C63 | 115.44 (19) | C41—C46—H46 | 119.7 |
C5—C6—C63 | 123.10 (19) | N51—C51—C5 | 178.2 (3) |
C7A—N7—C6 | 115.71 (19) | C62—N61—C67A | 108.84 (19) |
N7—C7A—N1 | 125.3 (2) | C62—N61—H61 | 125.6 |
N7—C7A—C3A | 127.5 (2) | C67A—N61—H61 | 125.6 |
N1—C7A—C3A | 107.14 (19) | N61—C62—C63 | 110.7 (2) |
C16—C11—C12 | 121.2 (2) | N61—C62—H62 | 124.7 |
C16—C11—N1 | 119.0 (2) | C63—C62—H62 | 124.7 |
C12—C11—N1 | 119.9 (2) | C62—C63—C63A | 105.77 (19) |
C13—C12—C11 | 119.2 (2) | C62—C63—C6 | 128.0 (2) |
C13—C12—H12 | 120.4 | C63A—C63—C6 | 125.76 (19) |
C11—C12—H12 | 120.4 | C64—C63A—C67A | 118.5 (2) |
C12—C13—C14 | 120.1 (2) | C64—C63A—C63 | 134.5 (2) |
C12—C13—H13 | 120.0 | C67A—C63A—C63 | 106.96 (19) |
C14—C13—H13 | 120.0 | C65—C64—C63A | 118.7 (2) |
C15—C14—C13 | 120.3 (2) | C65—C64—H64 | 120.7 |
C15—C14—H14 | 119.9 | C63A—C64—H64 | 120.7 |
C13—C14—H14 | 119.9 | C64—C65—C66 | 121.5 (2) |
C14—C15—C16 | 120.2 (2) | C64—C65—H65 | 119.2 |
C14—C15—H15 | 119.9 | C66—C65—H65 | 119.2 |
C16—C15—H15 | 119.9 | C67—C66—C65 | 121.2 (2) |
C11—C16—C15 | 119.1 (2) | C67—C66—H66 | 119.4 |
C11—C16—H16 | 120.4 | C65—C66—H66 | 119.4 |
C15—C16—H16 | 120.4 | C66—C67—C67A | 116.9 (2) |
C3—C31—H31A | 109.5 | C66—C67—H67 | 121.5 |
C3—C31—H31B | 109.5 | C67A—C67—H67 | 121.5 |
H31A—C31—H31B | 109.5 | N61—C67A—C67 | 129.2 (2) |
C3—C31—H31C | 109.5 | N61—C67A—C63A | 107.7 (2) |
H31A—C31—H31C | 109.5 | C67—C67A—C63A | 123.1 (2) |
H31B—C31—H31C | 109.5 | ||
C7A—N1—N2—C3 | −0.3 (2) | N1—C11—C16—C15 | −177.2 (2) |
C11—N1—N2—C3 | 176.09 (19) | C14—C15—C16—C11 | −0.6 (4) |
N1—N2—C3—C3A | −0.1 (2) | C3A—C4—C41—C42 | −112.1 (3) |
N1—N2—C3—C31 | 177.51 (19) | C5—C4—C41—C42 | 69.0 (3) |
N2—C3—C3A—C4 | 174.5 (3) | C3A—C4—C41—C46 | 66.5 (3) |
C31—C3—C3A—C4 | −2.8 (5) | C5—C4—C41—C46 | −112.3 (3) |
N2—C3—C3A—C7A | 0.4 (2) | C46—C41—C42—F42 | −179.4 (2) |
C31—C3—C3A—C7A | −176.9 (2) | C4—C41—C42—F42 | −0.6 (3) |
C7A—C3A—C4—C5 | −1.0 (3) | C46—C41—C42—C43 | −0.6 (4) |
C3—C3A—C4—C5 | −174.5 (2) | C4—C41—C42—C43 | 178.2 (2) |
C7A—C3A—C4—C41 | −179.9 (2) | F42—C42—C43—C44 | −179.7 (2) |
C3—C3A—C4—C41 | 6.6 (4) | C41—C42—C43—C44 | 1.5 (4) |
C3A—C4—C5—C6 | −5.4 (3) | C42—C43—C44—C45 | −1.0 (4) |
C41—C4—C5—C6 | 173.5 (2) | C43—C44—C45—C46 | −0.3 (4) |
C3A—C4—C5—C51 | 173.0 (2) | C44—C45—C46—C41 | 1.3 (4) |
C41—C4—C5—C51 | −8.1 (3) | C42—C41—C46—C45 | −0.8 (3) |
C4—C5—C6—N7 | 7.2 (3) | C4—C41—C46—C45 | −179.6 (2) |
C51—C5—C6—N7 | −171.1 (2) | C67A—N61—C62—C63 | −0.6 (3) |
C4—C5—C6—C63 | −169.7 (2) | N61—C62—C63—C63A | 0.2 (3) |
C51—C5—C6—C63 | 11.9 (3) | N61—C62—C63—C6 | 172.3 (2) |
C5—C6—N7—C7A | −1.8 (3) | N7—C6—C63—C62 | −150.6 (2) |
C63—C6—N7—C7A | 175.36 (19) | C5—C6—C63—C62 | 26.5 (4) |
C6—N7—C7A—N1 | 178.1 (2) | N7—C6—C63—C63A | 20.0 (3) |
C6—N7—C7A—C3A | −5.3 (3) | C5—C6—C63—C63A | −162.9 (2) |
N2—N1—C7A—N7 | 177.7 (2) | C62—C63—C63A—C64 | −177.7 (2) |
C11—N1—C7A—N7 | 1.7 (4) | C6—C63—C63A—C64 | 10.0 (4) |
N2—N1—C7A—C3A | 0.6 (2) | C62—C63—C63A—C67A | 0.2 (3) |
C11—N1—C7A—C3A | −175.4 (2) | C6—C63—C63A—C67A | −172.1 (2) |
C4—C3A—C7A—N7 | 6.9 (3) | C67A—C63A—C64—C65 | 0.6 (3) |
C3—C3A—C7A—N7 | −177.7 (2) | C63—C63A—C64—C65 | 178.3 (2) |
C4—C3A—C7A—N1 | −176.06 (19) | C63A—C64—C65—C66 | 0.6 (4) |
C3—C3A—C7A—N1 | −0.6 (2) | C64—C65—C66—C67 | −1.6 (4) |
C7A—N1—C11—C16 | 131.2 (2) | C65—C66—C67—C67A | 1.2 (3) |
N2—N1—C11—C16 | −44.5 (3) | C62—N61—C67A—C67 | 179.3 (2) |
C7A—N1—C11—C12 | −47.4 (3) | C62—N61—C67A—C63A | 0.6 (3) |
N2—N1—C11—C12 | 136.9 (2) | C66—C67—C67A—N61 | −178.4 (2) |
C16—C11—C12—C13 | −0.7 (3) | C66—C67—C67A—C63A | 0.1 (3) |
N1—C11—C12—C13 | 177.8 (2) | C64—C63A—C67A—N61 | 177.75 (19) |
C11—C12—C13—C14 | −0.6 (4) | C63—C63A—C67A—N61 | −0.5 (3) |
C12—C13—C14—C15 | 1.3 (4) | C64—C63A—C67A—C67 | −1.0 (3) |
C13—C14—C15—C16 | −0.7 (4) | C63—C63A—C67A—C67 | −179.3 (2) |
C12—C11—C16—C15 | 1.3 (4) |
D—H···A | D—H | H···A | D···A | D—H···A |
N61—H61···N2i | 0.88 | 2.10 | 2.953 (3) | 163 |
C46—H46···N7ii | 0.95 | 2.55 | 3.469 (3) | 164 |
C67—H67···Cgi | 0.95 | 2.77 | 3.652 (2) | 155 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1/2, −y+1/2, −z+1. |
Experimental details
Crystal data | |
Chemical formula | C28H18FN5 |
Mr | 443.47 |
Crystal system, space group | Monoclinic, C2/c |
Temperature (K) | 120 |
a, b, c (Å) | 24.155 (3), 10.5830 (7), 18.712 (3) |
β (°) | 105.743 (10) |
V (Å3) | 4604.0 (10) |
Z | 8 |
Radiation type | Mo Kα |
µ (mm−1) | 0.08 |
Crystal size (mm) | 0.45 × 0.26 × 0.25 |
Data collection | |
Diffractometer | Bruker Nonius KappaCCD diffractometer |
Absorption correction | Multi-scan (SADABS; Sheldrick, 2003) |
Tmin, Tmax | 0.968, 0.979 |
No. of measured, independent and observed [I > 2σ(I)] reflections | 51259, 5280, 3346 |
Rint | 0.065 |
(sin θ/λ)max (Å−1) | 0.650 |
Refinement | |
R[F2 > 2σ(F2)], wR(F2), S | 0.069, 0.211, 1.10 |
No. of reflections | 5280 |
No. of parameters | 308 |
H-atom treatment | H-atom parameters constrained |
Δρmax, Δρmin (e Å−3) | 0.38, −0.29 |
Computer programs: COLLECT (Hooft, 1999), DIRAX/LSQ (Duisenberg et al., 2000), EVALCCD (Duisenberg et al., 2003), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008) and PLATON (Spek, 2009).
N2—N1—C11—C12 | 136.9 (2) | C5—C6—C63—C63A | −162.9 (2) |
C3A—C4—C41—C42 | −112.1 (3) |
D—H···A | D—H | H···A | D···A | D—H···A |
N61—H61···N2i | 0.88 | 2.10 | 2.953 (3) | 163 |
C46—H46···N7ii | 0.95 | 2.55 | 3.469 (3) | 164 |
C67—H67···Cgi | 0.95 | 2.77 | 3.652 (2) | 155 |
Symmetry codes: (i) x, y+1, z; (ii) −x+1/2, −y+1/2, −z+1. |
We report here the structure of the title compound, (I), which we compare with the three analogues (II)–(IV) (see Scheme) whose structures were reported fairly recently (Low et al., 2007). As in the synthesis of compounds (II)–(IV), compound (I) was prepared by a multicomponent condensation reaction between 5-amino-3-methyl-1-henylpyrazole [phenyl?], 3-(2-cyanoacetyl)indole and an aryl aldehyde, here 2-fluorobenzaldehyde, using microwave irradiation under solvent-free conditions. This method has been developed (Quiroga et al., 2007) as a route for the introduction of an indolyl residue into substituted pyrazolo[3,4-b]pyridines, in order to assess the influence of the naturally occurring indolyl group on the biological activity of the resulting synthetic products. The crystallization characteristics of compounds (I)–(IV) show some interesting variations, which cannot be readily predicted or explained. Compounds (I) and (II) both crystallize in space group C2/c, while (II) ? and (IV) both crystallize in P1: however, while compounds (II) and (III) crystallize as stoichiometric 1:1 solvates with dimethylformamide, both (I) and (IV) crystallize in solvent-free forms.
The pyrazolopyridine component of the molecule of (I) is effectively planar, with the maximum deviation from the mean plane that of atom C5, 0.067 (2) Å; this slight deviation may be associated with the presence of three adjacent substituents, two of them bulky, at atoms C4–C6. It is interesting to note that the displacement of atom C51 from the mean plane of the bicyclic ring system, 0.270 (2) Å, is in the direction opposite from those of the displacements of C41 and C63, -0.053 (2) Å and -0.174 (2) Å, respectively, indicating that non-bonded repulsions between these substituents are probably the cause of the displacements. Due to this effective planarity, the molecular conformation can therefore be described in terms of just the three torsional angles (Table 1) defining the orientation of the substituents relative to the pyrazolopyridine unit. The dihedral angles between the mean planes of the substituents and that of the pyrazolopyridine unit are, for the unsubstituted phenyl ring at N1, 45.6 (2)°, for the substituted phenyl ring at C4, 70.8 (2)°, and for the indolyl unit at C6, 25.1 (2)°. Accordingly, the molecule of (I) has no internal symmetry and thus it is conformationally chiral, although the centrosymmetric space group accommodates equal numbers of the two conformational enantiomers. The bond distances and angles within the molecule of compound (I) show no unexpected values.
Three independent hydrogen bonds, one each of N—H···N, C—H···N and C—H···π(arene) types (Table 2), link the molecules of (I) into a complex chain of rings, or molecular ladder. The N—H···N hydrogen bond links molecules related by translation into a C(9) (Bernstein et al., 1995) chain running parallel to the [010] direction; this chain formation is augmented by the C—H···π(arene) hydrogen bond, so forming a chain of rings along [010]. Pairs of antiparallel chains, related to one another by inversion, are then linked by paired C—H···N hydrogen bonds to form a complex chain of edge-fused rings in which R22(14) rings centred at (1/4, n + 1/4, 1/2), where n represents an integer, alternate with R44(26) rings centred at (1/4, n - 1/4, 1/2) where n again represents an integer (Fig. 2). The formation of the chain is weakly augmented by a π···π stacking interaction involving pairs of pyridine rings: the pyridyl rings of the molecules at (x, y, z) and (1/2 - x, 1/2, - y, 1 - z), which form the R22(14) motif, are strictly parallel with an interplanar spacing of 3.674 (2) Å; the ring–centroid separation is 3.840 (2) Å, corresponding to a ring–centroid offset of 1.117 (2) Å.
Four chains of this type run through each unit cell, along the lines (1/4, y, 0), (1/4, y, 1/2), (3/4, y, 0) and (3/4, y, 1/2) (Fig. 3): there are no direction-specific interactions between adjacent chains, but instead these chains enclose cavities, totalling ca 9% of the unit-cell volume. There are four symmetry-related cavities per unit cell, each of volume ca 104 Å3, located on twofold rotation axes and centred close to (0, 0.335, 1/4), (0. 0.665, 3/4), (1/2, 0.835, 1/4) and (1/2, 0.165, 3/4). Each cavity is bounded by a number of aromatic C—H bonds, along with F atoms and the N atoms belonging to nitrile units (Fig. 3). While significant electron density is located within the cavities, calculated by the SQUEEZE option in PLATON (Spek, 2009) as 7 electrons per cavity, it did not prove possible to reconcile the distribution of electron density with any plausible array of disordered solvent molecules.
The supramolecular aggregation in compound (I) differs markedly from that observed for compounds (II) and (III) (Low et al., 2007) as in these structures the single N—H bond is engaged in a hydrogen bond to the dimethylformamide component. Thus, in compound (II), a single C—H···π(arene) hydrogen bond links the pyrazolopyridine units into centrosymmetric dimers from which the dimethylformamide units are pendent, while in compound (III), a combination of C—H···N and C—H···π(arene) hydrogen bonds links the pyrazolopyridine units into a chain containing two types of ring, again with pendent solvent molecules. By contrast, the molecules of compound (IV), where no solvent component is present, are linked into simple C(12) chains by an N—H···O hydrogen bond. Hence, the hydrogen-bonding behaviour is different in each of compounds (I)–(IV). On the other hand, all four compounds exhibit a π···π stacking interaction involving the pyridyl rings in pairs of molecules related by inversion. In compound (II), as in (I), this interaction augments the formation of a hydrogen-bonded dimer unit, in (III) it augments the chain formation, and in compound (IV), this interaction links a pair of antiparallel C(12) chains.