Compounds (I) and (II) were prepared in polycrystalline form in the Department
of Medicinal Chemistry under Professor V·G. Granik, State Scientific
Center "NIOPIK", according to the procedure of Ryabova et al. (2001).
During the exposures, each specimen was spun in its plane to improve particle
statistics. The unit-cell dimensions were determined from the Guinier
photographs with the indexing program ITO (Visser, 1969) and refined with the
program LSPAID (Visser, 1986) to M20 = 20 and F30 = 49 (0.010, 57)
for (I) and M20 = 37 and F30 = 89 (0.008, 43) for (II), using the
first 50 peak positions. The space groups P21/n and Pbca were
chosen on the basis of systematic extinction rules for (I) and (II),
respectively. Intensities for the structure determination and refinement were
measured from the Guinier photographs in 0.01° steps using a Johannson LS18
line scanner. The structures of (I) and (II) were solved by the grid search
procedure (Chernyshev & Schenk, 1998). Preliminary information about the
possible structures of (I) and (II) was obtained from IR and NMR spectroscopy
and mass spectrometry. The approximate models of the molecules were built up
with the program MOPAC6.0 (Stewart, 1990). There are two independent molecules
in the crystal structure of (I). However, the careful inspection of the
results of full-pattern-decomposition procedure show the presence of pseudo C
centering. The full-pattern-decomposition procedure was undertaken again in
the space group C2/c to take into account the intensities of the
most of peaks, though gave the worse profile R-factor, Rwp =
0.089 compared with Rwp = 0.064 for P21/n. The
crystal structure of (I) was solved in space group C2/c and
refined in the correct space group P21/n. The conformations of
two independent molecules of (I) and one molecule of (II) changed during the
subsequent bond-restrained Rietveld refinements. The strength of the
restraints was a function of interatomic separation and for intramolecular
bond lengths corresponds to an r.m.s. deviation of 0.03 Å. The additional
restraints were applied to the planarity of the phenyl rings and tricyclic
fragments. The diffraction profiles and the differences between the measured
and calculated profiles are shown on Fig. 4. No atomic displacement parameters
were refined for (I), and the overall Uiso parameter for non–H atoms
was refined for (II). H atoms were placed in geometrically calculated
positions and allowed to refine using bond restraints, with a common isotropic
displacement parameter Uiso fixed to 0.05 Å2. The March–Dollase
texture formalism (Dollase, 1986) with 100 as a direction of preferred
orientation was applied for (II). The texture parameter r refined to 1.26 (2).
The crystal structure of (I) contains a void centered at (0,0,0) with a volume
of 44 Å3. However, no peaks in the difference Fourier map were located in
this area and when O atom was placed in this position, its occupancy factor
was refined to zero.
For both compounds, data collection: Johannson LS18 linescanner data collection program; cell refinement: LSPAID (Visser et al., 1986); data reduction: Philips Profile Fit 1.0b (Philips, 1996); program(s) used to solve structure: MRIA (Chernyshev & Zlokazov, 1992); program(s) used to refine structure: MRIA; molecular graphics: PLUTON (Spek, 1992); software used to prepare material for publication: MRIA, SHELXL93 (Sheldrick, 1993) and PARST (Nardelli, 1983).
(I) 1-(4-Nitrophenyl)-2-phenylimino-2,5-dihydro-1
H-pyrido[3,2-
b]indole-3- carbonitrile
top
Crystal data top
C24H15N5O2 | F(000) = 1680 |
Mr = 405.41 | Dx = 1.288 Mg m−3 |
Monoclinic, P21/n | Melting point = 478–479 K |
a = 16.131 (7) Å | Cu Kα1 radiation, λ = 1.54059 Å |
b = 18.070 (8) Å | µ = 0.70 mm−1 |
c = 14.349 (6) Å | T = 295 K |
β = 91.95 (2)° | Particle morphology: parallelepiped |
V = 4180 (3) Å3 | red |
Z = 8 | flat_sheet, 7 × 7 mm |
Data collection top
Enraf-Nonius Guinier Johannson camera FR 552 diffractometer | Specimen mounting: pressed as a thin layer in the specimen holder of the camera |
Radiation source: Fine focus X-ray tube, Nonius 3502.223 | Data collection mode: transmission |
Quartz monochromator | Scan method: Stationary detector |
Refinement top
Refinement on Inet | Profile function: split-type pseudo-Voigt (Toraya, 1986) |
Least-squares matrix: full with fixed elements per cycle | 312 parameters |
Rp = 0.060 | 315 restraints |
Rwp = 0.084 | 0 constraints |
Rexp = 0.034 | H atoms treated by a mixture of independent and constrained refinement |
χ2 = 6.250 | Weighting scheme based on measured s.u.'s |
7101 data points | (Δ/σ)max = 0.025 |
Excluded region(s): 4.00 - 5.99 | Background function: Chebyshev polynomial up to the 5th order |
Crystal data top
C24H15N5O2 | V = 4180 (3) Å3 |
Mr = 405.41 | Z = 8 |
Monoclinic, P21/n | Cu Kα1 radiation, λ = 1.54059 Å |
a = 16.131 (7) Å | µ = 0.70 mm−1 |
b = 18.070 (8) Å | T = 295 K |
c = 14.349 (6) Å | flat_sheet, 7 × 7 mm |
β = 91.95 (2)° | |
Data collection top
Enraf-Nonius Guinier Johannson camera FR 552 diffractometer | Data collection mode: transmission |
Specimen mounting: pressed as a thin layer in the specimen holder of the camera | Scan method: Stationary detector |
Refinement top
Rp = 0.060 | 7101 data points |
Rwp = 0.084 | 312 parameters |
Rexp = 0.034 | 315 restraints |
χ2 = 6.250 | H atoms treated by a mixture of independent and constrained refinement |
Special details top
Experimental. specimen was rotated in its plane |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1A | 0.6297 (17) | 0.3683 (15) | −0.1053 (16) | 0.051* | |
C2A | 0.5794 (15) | 0.3154 (14) | −0.152 (2) | 0.051* | |
C3A | 0.5954 (16) | 0.2936 (15) | −0.243 (2) | 0.051* | |
C4A | 0.6635 (17) | 0.3232 (15) | −0.2894 (17) | 0.051* | |
C5A | 0.7130 (16) | 0.3759 (14) | −0.2424 (19) | 0.051* | |
C6A | 0.6971 (17) | 0.3983 (14) | −0.151 (2) | 0.051* | |
N7A | 0.7807 (14) | 0.4125 (12) | −0.2717 (15) | 0.051* | |
C8A | 0.7577 (16) | 0.4506 (14) | −0.125 (2) | 0.051* | |
C9A | 0.8081 (16) | 0.4582 (13) | −0.202 (2) | 0.051* | |
N10A | 0.7725 (13) | 0.4911 (13) | −0.0446 (16) | 0.051* | |
C11A | 0.8760 (16) | 0.5058 (16) | −0.1996 (19) | 0.051* | |
C12A | 0.8390 (17) | 0.5400 (15) | −0.040 (2) | 0.051* | |
C13A | 0.8910 (17) | 0.5474 (14) | −0.118 (2) | 0.051* | |
C14A | 0.7271 (16) | 0.4795 (15) | 0.033 (2) | 0.051* | |
C15A | 0.6613 (18) | 0.5270 (15) | 0.053 (2) | 0.051* | |
C16A | 0.6166 (17) | 0.5167 (16) | 0.135 (2) | 0.051* | |
C17A | 0.6359 (15) | 0.4588 (14) | 0.1993 (19) | 0.051* | |
C18A | 0.7042 (17) | 0.4115 (15) | 0.180 (2) | 0.051* | |
C19A | 0.7489 (16) | 0.4231 (15) | 0.098 (2) | 0.051* | |
N20A | 0.8560 (13) | 0.5674 (12) | 0.0406 (16) | 0.051* | |
C21A | 0.9040 (16) | 0.6298 (15) | 0.055 (2) | 0.051* | |
C22A | 0.8840 (15) | 0.6995 (16) | 0.0180 (19) | 0.051* | |
C23A | 0.9348 (18) | 0.7613 (15) | 0.038 (2) | 0.051* | |
C24A | 1.0061 (16) | 0.7534 (14) | 0.096 (2) | 0.051* | |
C25A | 1.0261 (16) | 0.6836 (15) | 0.1333 (19) | 0.051* | |
C26A | 0.9741 (17) | 0.6223 (14) | 0.114 (2) | 0.051* | |
N27A | 0.5909 (13) | 0.4512 (12) | 0.2852 (17) | 0.051* | |
O28A | 0.5345 (11) | 0.4958 (9) | 0.2931 (11) | 0.051* | |
O29A | 0.6165 (12) | 0.4034 (11) | 0.3378 (16) | 0.051* | |
C30A | 0.9694 (15) | 0.5758 (13) | −0.1063 (18) | 0.051* | |
N31A | 1.0373 (11) | 0.5918 (9) | −0.0848 (13) | 0.051* | |
H32A | 0.802 (10) | 0.408 (9) | −0.325 (12) | 0.051* | |
H33A | 0.618 (10) | 0.383 (9) | −0.045 (11) | 0.051* | |
H34A | 0.534 (10) | 0.296 (9) | −0.122 (11) | 0.051* | |
H35A | 0.562 (9) | 0.259 (9) | −0.273 (12) | 0.051* | |
H36A | 0.675 (10) | 0.309 (9) | −0.350 (12) | 0.051* | |
H37A | 0.910 (9) | 0.510 (9) | −0.251 (12) | 0.051* | |
H38A | 0.647 (9) | 0.564 (9) | 0.011 (12) | 0.051* | |
H39A | 0.573 (10) | 0.549 (9) | 0.144 (12) | 0.051* | |
H40A | 0.720 (10) | 0.373 (8) | 0.220 (12) | 0.051* | |
H41A | 0.792 (9) | 0.392 (9) | 0.084 (12) | 0.051* | |
H42A | 0.837 (9) | 0.706 (9) | −0.021 (12) | 0.051* | |
H43A | 0.922 (10) | 0.807 (8) | 0.012 (13) | 0.051* | |
H44A | 1.040 (10) | 0.794 (9) | 0.109 (13) | 0.051* | |
H45A | 1.073 (9) | 0.678 (9) | 0.172 (12) | 0.051* | |
H46A | 0.987 (10) | 0.577 (8) | 0.141 (11) | 0.051* | |
C1B | 0.1664 (17) | −0.1714 (16) | −0.09440 (18) | 0.051* | |
C2B | 0.1224 (16) | −0.2285 (13) | −0.1406 (2) | 0.051* | |
C3B | 0.1303 (16) | −0.2408 (14) | −0.2365 (2) | 0.051* | |
C4B | 0.1822 (17) | −0.1949 (14) | −0.28810 (18) | 0.051* | |
C5B | 0.2251 (15) | −0.1377 (14) | −0.2412 (2) | 0.051* | |
C6B | 0.2177 (15) | −0.1251 (14) | −0.1455 (2) | 0.051* | |
N7B | 0.2778 (14) | −0.0869 (12) | −0.27540 (15) | 0.051* | |
C8B | 0.2687 (17) | −0.0645 (14) | −0.1212 (2) | 0.051* | |
C9B | 0.3044 (16) | −0.0422 (15) | −0.2039 (2) | 0.051* | |
N10B | 0.2868 (14) | −0.0282 (12) | −0.03850 (16) | 0.051* | |
C11B | 0.3593 (16) | 0.0172 (16) | −0.20630 (19) | 0.051* | |
C12B | 0.3407 (17) | 0.0314 (15) | −0.0379 (2) | 0.051* | |
C13B | 0.3783 (17) | 0.0539 (14) | −0.1217 (2) | 0.051* | |
C14B | 0.2568 (15) | −0.0564 (15) | 0.0430 (2) | 0.051* | |
C15B | 0.1815 (17) | −0.0294 (15) | 0.0752 (2) | 0.051* | |
C16B | 0.1515 (16) | −0.0581 (16) | 0.1591 (2) | 0.051* | |
C17B | 0.1963 (17) | −0.1092 (14) | 0.2168 (2) | 0.051* | |
C18B | 0.2730 (17) | −0.1374 (13) | 0.1840 (2) | 0.051* | |
C19B | 0.3024 (17) | −0.1077 (15) | 0.0988 (2) | 0.051* | |
N20B | 0.3497 (12) | 0.0668 (11) | 0.03920 (15) | 0.051* | |
C21B | 0.4004 (17) | 0.1281 (15) | 0.0478 (2) | 0.051* | |
C22B | 0.3749 (15) | 0.1994 (15) | 0.0216 (2) | 0.051* | |
C23B | 0.4292 (18) | 0.2600 (14) | 0.0337 (2) | 0.051* | |
C24B | 0.5083 (16) | 0.2498 (14) | 0.0755 (2) | 0.051* | |
C25B | 0.5341 (17) | 0.1786 (14) | 0.1020 (2) | 0.051* | |
C26B | 0.4794 (17) | 0.1181 (14) | 0.0897 (2) | 0.051* | |
N27B | 0.1602 (12) | −0.1334 (11) | 0.30420 (15) | 0.051* | |
O28B | 0.1059 (12) | −0.0918 (11) | 0.33100 (16) | 0.051* | |
O29B | 0.1890 (17) | −0.1882 (15) | 0.34140 (15) | 0.051* | |
C30B | 0.4553 (13) | 0.0930 (13) | −0.12580 (15) | 0.051* | |
N31B | 0.5142 (11) | 0.1273 (10) | −0.14430 (12) | 0.051* | |
H32B | 0.292 (10) | −0.083 (9) | −0.3325 (12) | 0.051* | |
H33B | 0.161 (10) | −0.164 (10) | −0.0307 (11) | 0.051* | |
H34B | 0.088 (10) | −0.259 (10) | −0.1069 (12) | 0.051* | |
H35B | 0.100 (10) | −0.278 (8) | −0.2660 (12) | 0.051* | |
H36B | 0.187 (10) | −0.202 (9) | −0.3519 (12) | 0.051* | |
H37B | 0.382 (9) | 0.030 (9) | −0.2628 (12) | 0.051* | |
H38B | 0.152 (10) | 0.004 (9) | 0.0387 (12) | 0.051* | |
H39B | 0.101 (9) | −0.037 (9) | 0.1763 (12) | 0.051* | |
H40B | 0.307 (11) | −0.171 (9) | 0.2177 (13) | 0.051* | |
H41B | 0.352 (9) | −0.125 (9) | 0.0768 (12) | 0.051* | |
H42B | 0.322 (9) | 0.207 (8) | −0.0048 (12) | 0.051* | |
H43B | 0.412 (10) | 0.307 (8) | 0.0150 (13) | 0.051* | |
H44B | 0.544 (9) | 0.290 (9) | 0.0833 (12) | 0.051* | |
H45B | 0.586 (9) | 0.171 (9) | 0.1298 (12) | 0.051* | |
H46B | 0.497 (11) | 0.071 (8) | 0.1091 (12) | 0.051* | |
Geometric parameters (Å, º) top
C1A—C2A | 1.41 (4) | C1B—C2B | 1.41 (4) |
C1A—C6A | 1.40 (4) | C1B—C6B | 1.40 (4) |
C1A—H33A | 0.93 (16) | C1B—H33B | 0.93 (16) |
C2A—C3A | 1.40 (4) | C2B—C3B | 1.40 (4) |
C2A—H34A | 0.93 (16) | C2B—H34B | 0.93 (17) |
C3A—C4A | 1.41 (4) | C3B—C4B | 1.41 (4) |
C3A—H35A | 0.93 (15) | C3B—H35B | 0.93 (16) |
C4A—C5A | 1.40 (4) | C4B—C5B | 1.40 (4) |
C4A—H36A | 0.93 (17) | C4B—H36B | 0.93 (17) |
C5A—C6A | 1.40 (4) | C5B—C6B | 1.40 (4) |
C5A—N7A | 1.36 (3) | C5B—N7B | 1.35 (3) |
C6A—C8A | 1.40 (4) | C6B—C8B | 1.41 (4) |
N7A—C9A | 1.36 (3) | N7B—C9B | 1.36 (4) |
N7A—H32A | 0.86 (18) | N7B—H32B | 0.86 (17) |
C8A—C9A | 1.40 (4) | C8B—C9B | 1.40 (4) |
C8A—N10A | 1.38 (4) | C8B—N10B | 1.38 (4) |
C9A—C11A | 1.39 (4) | C9B—C11B | 1.39 (4) |
N10A—C12A | 1.39 (4) | N10B—C12B | 1.38 (4) |
N10A—C14A | 1.37 (4) | N10B—C14B | 1.38 (4) |
C11A—C13A | 1.41 (4) | C11B—C13B | 1.41 (4) |
C11A—H37A | 0.93 (17) | C11B—H37B | 0.93 (18) |
C12A—C13A | 1.42 (4) | C12B—C13B | 1.42 (4) |
C12A—N20A | 1.28 (4) | C12B—N20B | 1.28 (4) |
C13A—C30A | 1.37 (4) | C13B—C30B | 1.43 (3) |
C14A—C15A | 1.40 (4) | C14B—C15B | 1.40 (4) |
C14A—C19A | 1.41 (4) | C14B—C19B | 1.41 (4) |
C15A—C16A | 1.41 (4) | C15B—C16B | 1.41 (4) |
C15A—H38A | 0.93 (17) | C15B—H38B | 0.93 (16) |
C16A—C17A | 1.43 (4) | C16B—C17B | 1.42 (4) |
C16A—H39A | 0.93 (16) | C16B—H39B | 0.94 (16) |
C17A—C18A | 1.43 (4) | C17B—C18B | 1.43 (4) |
C17A—N27A | 1.46 (4) | C17B—N27B | 1.47 (4) |
C18A—C19A | 1.42 (4) | C18B—C19B | 1.43 (4) |
C18A—H40A | 0.93 (16) | C18B—H40B | 0.93 (17) |
C19A—H41A | 0.93 (16) | C19B—H41B | 0.93 (15) |
N20A—C21A | 1.38 (3) | N20B—C21B | 1.38 (3) |
C21A—C22A | 1.40 (4) | C21B—C22B | 1.40 (4) |
C21A—C26A | 1.40 (4) | C21B—C26B | 1.40 (4) |
C22A—C23A | 1.41 (4) | C22B—C23B | 1.41 (4) |
C22A—H42A | 0.93 (16) | C22B—H42B | 0.93 (15) |
C23A—C24A | 1.40 (4) | C23B—C24B | 1.40 (4) |
C23A—H43A | 0.93 (16) | C23B—H43B | 0.93 (15) |
C24A—C25A | 1.40 (4) | C24B—C25B | 1.40 (4) |
C24A—H44A | 0.93 (16) | C24B—H44B | 0.93 (15) |
C25A—C26A | 1.41 (4) | C25B—C26B | 1.41 (4) |
C25A—H45A | 0.93 (15) | C25B—H45B | 0.93 (15) |
C26A—H46A | 0.93 (15) | C26B—H46B | 0.93 (15) |
N27A—O28A | 1.22 (3) | N27B—O28B | 1.23 (3) |
N27A—O29A | 1.21 (3) | N27B—O29B | 1.21 (3) |
C30A—N31A | 1.16 (3) | C30B—N31B | 1.17 (3) |
| | | |
C6A—C1A—H33A | 120 (10) | C6B—C1B—H33B | 120 (10) |
C2A—C1A—H33A | 121 (10) | C2B—C1B—H33B | 120 (10) |
C2A—C1A—C6A | 119 (2) | C2B—C1B—C6B | 119 (2) |
C1A—C2A—H34A | 120 (10) | C1B—C2B—H34B | 120 (10) |
C1A—C2A—C3A | 121 (2) | C1B—C2B—C3B | 121 (3) |
C3A—C2A—H34A | 120 (10) | C3B—C2B—H34B | 119 (10) |
C2A—C3A—H35A | 120 (11) | C2B—C3B—H35B | 120 (10) |
C2A—C3A—C4A | 120 (3) | C2B—C3B—C4B | 120 (3) |
C4A—C3A—H35A | 120 (9) | C4B—C3B—H35B | 120 (10) |
C3A—C4A—H36A | 121 (11) | C3B—C4B—H36B | 121 (10) |
C3A—C4A—C5A | 118 (2) | C3B—C4B—C5B | 118 (2) |
C5A—C4A—H36A | 121 (10) | C5B—C4B—H36B | 121 (10) |
C4A—C5A—N7A | 129 (2) | C4B—C5B—N7B | 129 (2) |
C4A—C5A—C6A | 121 (2) | C4B—C5B—C6B | 122 (2) |
C6A—C5A—N7A | 109 (2) | C6B—C5B—N7B | 109 (2) |
C1A—C6A—C5A | 120 (3) | C1B—C6B—C5B | 119 (2) |
C5A—C6A—C8A | 107 (2) | C5B—C6B—C8B | 108 (2) |
C1A—C6A—C8A | 133 (3) | C1B—C6B—C8B | 133 (2) |
C5A—N7A—H32A | 126 (12) | C5B—N7B—H32B | 126 (11) |
C5A—N7A—C9A | 108 (2) | C5B—N7B—C9B | 108 (2) |
C9A—N7A—H32A | 126 (12) | C9B—N7B—H32B | 125 (11) |
C6A—C8A—N10A | 133 (3) | C6B—C8B—N10B | 134 (3) |
C6A—C8A—C9A | 106 (2) | C6B—C8B—C9B | 106 (2) |
C9A—C8A—N10A | 121 (3) | C9B—C8B—N10B | 121 (3) |
N7A—C9A—C8A | 110 (2) | N7B—C9B—C8B | 110 (2) |
C8A—C9A—C11A | 122 (2) | C8B—C9B—C11B | 122 (2) |
N7A—C9A—C11A | 129 (2) | N7B—C9B—C11B | 128 (3) |
C8A—N10A—C14A | 121 (2) | C8B—N10B—C14B | 119 (2) |
C8A—N10A—C12A | 119 (2) | C8B—N10B—C12B | 119 (2) |
C12A—N10A—C14A | 119 (2) | C12B—N10B—C14B | 121 (2) |
C9A—C11A—H37A | 121 (10) | C9B—C11B—H37B | 119 (10) |
C9A—C11A—C13A | 117 (2) | C9B—C11B—C13B | 118 (2) |
C13A—C11A—H37A | 122 (11) | C13B—C11B—H37B | 123 (11) |
N10A—C12A—N20A | 116 (2) | N10B—C12B—N20B | 117 (2) |
N10A—C12A—C13A | 120 (2) | N10B—C12B—C13B | 120 (2) |
C13A—C12A—N20A | 124 (3) | C13B—C12B—N20B | 123 (3) |
C11A—C13A—C12A | 121 (3) | C11B—C13B—C12B | 120 (3) |
C12A—C13A—C30A | 121 (2) | C12B—C13B—C30B | 125 (2) |
C11A—C13A—C30A | 116 (2) | C11B—C13B—C30B | 111 (2) |
N10A—C14A—C19A | 121 (3) | N10B—C14B—C19B | 122 (3) |
N10A—C14A—C15A | 120 (2) | N10B—C14B—C15B | 119 (2) |
C15A—C14A—C19A | 119 (2) | C15B—C14B—C19B | 119 (2) |
C14A—C15A—H38A | 119 (10) | C14B—C15B—H38B | 119 (10) |
C14A—C15A—C16A | 120 (3) | C14B—C15B—C16B | 119 (2) |
C16A—C15A—H38A | 121 (11) | C16B—C15B—H38B | 122 (11) |
C15A—C16A—H39A | 117 (10) | C15B—C16B—H39B | 114 (10) |
C15A—C16A—C17A | 122 (3) | C15B—C16B—C17B | 124 (3) |
C17A—C16A—H39A | 121 (10) | C17B—C16B—H39B | 122 (10) |
C16A—C17A—N27A | 121 (2) | C16B—C17B—N27B | 119 (2) |
C16A—C17A—C18A | 118 (2) | C16B—C17B—C18B | 118 (2) |
C18A—C17A—N27A | 121 (2) | C18B—C17B—N27B | 123 (2) |
C17A—C18A—H40A | 122 (10) | C17B—C18B—H40B | 123 (11) |
C17A—C18A—C19A | 119 (2) | C17B—C18B—C19B | 118 (2) |
C19A—C18A—H40A | 119 (11) | C19B—C18B—H40B | 119 (11) |
C14A—C19A—C18A | 122 (3) | C14B—C19B—C18B | 123 (3) |
C18A—C19A—H41A | 119 (10) | C18B—C19B—H41B | 119 (10) |
C14A—C19A—H41A | 119 (10) | C14B—C19B—H41B | 118 (10) |
C12A—N20A—C21A | 123 (2) | C12B—N20B—C21B | 122 (2) |
N20A—C21A—C26A | 117 (2) | N20B—C21B—C26B | 118 (2) |
N20A—C21A—C22A | 124 (2) | N20B—C21B—C22B | 123 (2) |
C22A—C21A—C26A | 119 (2) | C22B—C21B—C26B | 119 (2) |
C21A—C22A—H42A | 120 (10) | C21B—C22B—H42B | 120 (10) |
C21A—C22A—C23A | 121 (3) | C21B—C22B—C23B | 120 (2) |
C23A—C22A—H42A | 119 (10) | C23B—C22B—H42B | 119 (10) |
C22A—C23A—H43A | 120 (10) | C22B—C23B—H43B | 120 (10) |
C22A—C23A—C24A | 120 (3) | C22B—C23B—C24B | 120 (2) |
C24A—C23A—H43A | 120 (11) | C24B—C23B—H43B | 120 (10) |
C23A—C24A—H44A | 120 (10) | C23B—C24B—H44B | 120 (10) |
C23A—C24A—C25A | 119 (2) | C23B—C24B—C25B | 120 (2) |
C25A—C24A—H44A | 120 (10) | C25B—C24B—H44B | 120 (10) |
C24A—C25A—H45A | 120 (10) | C24B—C25B—H45B | 120 (10) |
C24A—C25A—C26A | 120 (2) | C24B—C25B—C26B | 120 (2) |
C26A—C25A—H45A | 120 (10) | C26B—C25B—H45B | 120 (10) |
C21A—C26A—C25A | 120 (2) | C21B—C26B—C25B | 121 (2) |
C25A—C26A—H46A | 119 (9) | C25B—C26B—H46B | 119 (9) |
C21A—C26A—H46A | 120 (10) | C21B—C26B—H46B | 120 (10) |
C17A—N27A—O29A | 115 (2) | C17B—N27B—O29B | 118 (2) |
C17A—N27A—O28A | 114 (2) | C17B—N27B—O28B | 113 (2) |
O28A—N27A—O29A | 131 (2) | O28B—N27B—O29B | 129 (2) |
C13A—C30A—N31A | 169 (3) | C13B—C30B—N31B | 169 (2) |
| | | |
C16A—C17A—N27A—O28A | 3 (3) | C16B—C17B—N27B—O28B | −19 (3) |
C8A—N10A—C14A—C15A | −100 (3) | C8B—N10B—C14B—C15B | −94 (3) |
C9A—C11A—C13A—C30A | 161 (2) | C9B—C11B—C13B—C30B | 158 (2) |
C13A—C12A—N20A—C21A | 28 (4) | C13B—C12B—N20B—C21B | −3 (4) |
C12A—N20A—C21A—C22A | 61 (4) | C12B—N20B—C21B—C22B | 83 (3) |
Hydrogen-bond geometry (Å, º) top
D—H···A | D—H | H···A | D···A | D—H···A |
N7A—H32A···N20Bi | 0.86 (18) | 2.16 (18) | 2.99 (3) | 162 (16) |
N7B—H32B···N20Aii | 0.86 (17) | 2.15 (17) | 2.99 (3) | 166 (16) |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) x−1/2, −y+1/2, z−1/2. |
(II) 2-[(4-Nitrophenyl)-phenylamino]-5
H-pyrido[3,2-
b]indole-3-carbonitrile
top
Crystal data top
C24H15N5O2 | Dx = 1.396 Mg m−3 |
Mr = 405.41 | Melting point = 600–602 K |
Orthorhombic, Pbca | Cu Kα1 radiation, λ = 1.54059 Å |
a = 22.466 (8) Å | µ = 0.76 mm−1 |
b = 24.859 (9) Å | T = 295 K |
c = 6.906 (3) Å | Particle morphology: needles |
V = 3857 (3) Å3 | Yellow |
Z = 8 | flat_sheet, 7 × 7 mm |
F(000) = 1680 | |
Data collection top
Enraf-Nonius Guinier Johannson camera FR 552 diffractometer | Specimen mounting: pressed as a thin layer in the specimen holder of the camera |
Radiation source: Fine focus X-ray tube, Nonius 3502.223 | Data collection mode: transmission |
Quartz monochromator | Scan method: Stationary detector |
Refinement top
Refinement on Inet | 179 parameters |
Least-squares matrix: full with fixed elements per cycle | 151 restraints |
Rp = 0.060 | 30 constraints |
Rwp = 0.082 | H atoms treated by a mixture of independent and constrained refinement |
Rexp = 0.030 | Weighting scheme based on measured s.u.'s |
χ2 = 7.398 | (Δ/σ)max = 0.02 |
7501 data points | Background function: Chebyshev polynomial up to the 5th order |
Excluded region(s): 4.00 - 4.99 | Preferred orientation correction: March-Dollase (Dollase, 1986) |
Profile function: split-type pseudo-Voigt (Toraya, 1986) | |
Crystal data top
C24H15N5O2 | V = 3857 (3) Å3 |
Mr = 405.41 | Z = 8 |
Orthorhombic, Pbca | Cu Kα1 radiation, λ = 1.54059 Å |
a = 22.466 (8) Å | µ = 0.76 mm−1 |
b = 24.859 (9) Å | T = 295 K |
c = 6.906 (3) Å | flat_sheet, 7 × 7 mm |
Data collection top
Enraf-Nonius Guinier Johannson camera FR 552 diffractometer | Data collection mode: transmission |
Specimen mounting: pressed as a thin layer in the specimen holder of the camera | Scan method: Stationary detector |
Refinement top
Rp = 0.060 | 7501 data points |
Rwp = 0.082 | 179 parameters |
Rexp = 0.030 | 151 restraints |
χ2 = 7.398 | H atoms treated by a mixture of independent and constrained refinement |
Special details top
Experimental. specimen was rotated in its plane |
Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes)
are estimated using the full covariance matrix. The cell e.s.d.'s are taken
into account individually in the estimation of e.s.d.'s in distances, angles
and torsion angles; correlations between e.s.d.'s in cell parameters are only
used when they are defined by crystal symmetry. An approximate (isotropic)
treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s.
planes. |
Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å2) top | x | y | z | Uiso*/Ueq | |
C1 | 0.1759 (7) | 0.4555 (4) | −0.475 (2) | 0.081 (4)* | |
C2 | 0.2033 (7) | 0.4880 (6) | −0.6117 (15) | 0.081 (4)* | |
C3 | 0.2024 (7) | 0.5452 (6) | −0.5948 (15) | 0.081 (4)* | |
C4 | 0.1734 (7) | 0.5710 (5) | −0.4437 (17) | 0.081 (4)* | |
C5 | 0.1453 (7) | 0.5377 (6) | −0.3033 (17) | 0.081 (4)* | |
C6 | 0.1472 (7) | 0.4815 (5) | −0.3190 (16) | 0.081 (4)* | |
N7 | 0.1143 (6) | 0.5535 (4) | −0.1367 (15) | 0.081 (4)* | |
C8 | 0.1152 (7) | 0.4612 (6) | −0.1552 (15) | 0.081 (4)* | |
C9 | 0.0953 (7) | 0.5064 (5) | −0.0477 (16) | 0.081 (4)* | |
N10 | 0.1019 (6) | 0.4088 (4) | −0.0983 (11) | 0.081 (4)* | |
C11 | 0.0621 (7) | 0.4992 (6) | 0.1273 (15) | 0.081 (4)* | |
C12 | 0.0707 (7) | 0.4024 (5) | 0.0662 (15) | 0.081 (4)* | |
C13 | 0.0500 (7) | 0.4471 (5) | 0.1792 (15) | 0.081 (4)* | |
C14 | 0.1000 (6) | 0.3121 (6) | 0.1645 (14) | 0.081 (4)* | |
C15 | 0.1586 (7) | 0.3314 (5) | 0.2156 (16) | 0.081 (4)* | |
C16 | 0.2037 (7) | 0.2957 (6) | 0.2571 (15) | 0.081 (4)* | |
C17 | 0.1926 (7) | 0.2394 (5) | 0.2510 (17) | 0.081 (4)* | |
C18 | 0.1351 (6) | 0.2191 (5) | 0.1979 (17) | 0.081 (4)* | |
C19 | 0.0900 (6) | 0.2547 (5) | 0.1543 (15) | 0.081 (4)* | |
N20 | 0.0548 (6) | 0.3489 (4) | 0.1327 (13) | 0.081 (4)* | |
C21 | −0.0054 (7) | 0.3342 (4) | 0.0910 (16) | 0.081 (4)* | |
C22 | −0.0275 (8) | 0.3449 (6) | −0.0985 (16) | 0.081 (4)* | |
C23 | −0.0867 (7) | 0.3344 (6) | −0.1429 (14) | 0.081 (4)* | |
C24 | −0.1251 (6) | 0.3130 (6) | −0.0016 (17) | 0.081 (4)* | |
C25 | −0.1039 (7) | 0.3038 (5) | 0.1877 (16) | 0.081 (4)* | |
C26 | −0.0442 (6) | 0.3135 (6) | 0.2315 (16) | 0.081 (4)* | |
N27 | 0.2392 (5) | 0.2029 (4) | 0.2941 (14) | 0.081 (4)* | |
O28 | 0.2863 (4) | 0.2167 (3) | 0.3701 (9) | 0.081 (4)* | |
O29 | 0.2349 (4) | 0.1541 (7) | 0.2553 (10) | 0.081 (4)* | |
C30 | 0.0241 (5) | 0.4343 (4) | 0.3628 (15) | 0.081 (4)* | |
N31 | −0.0020 (5) | 0.4256 (3) | 0.5065 (13) | 0.081 (4)* | |
H32 | 0.109 (4) | 0.585 (3) | −0.101 (9) | 0.051* | |
H33 | 0.174 (4) | 0.417 (3) | −0.473 (9) | 0.051* | |
H34 | 0.224 (4) | 0.471 (3) | −0.723 (9) | 0.051* | |
H35 | 0.222 (4) | 0.568 (3) | −0.696 (9) | 0.051* | |
H36 | 0.170 (4) | 0.609 (3) | −0.420 (10) | 0.051* | |
H37 | 0.050 (4) | 0.530 (3) | 0.197 (9) | 0.051* | |
H38 | 0.163 (4) | 0.369 (3) | 0.219 (9) | 0.051* | |
H39 | 0.243 (4) | 0.308 (3) | 0.291 (10) | 0.051* | |
H40 | 0.130 (4) | 0.181 (3) | 0.193 (10) | 0.051* | |
H41 | 0.051 (4) | 0.244 (3) | 0.121 (9) | 0.051* | |
H42 | 0.002 (4) | 0.360 (3) | −0.186 (9) | 0.051* | |
H43 | −0.101 (4) | 0.342 (3) | −0.278 (11) | 0.051* | |
H44 | −0.168 (4) | 0.307 (3) | −0.032 (10) | 0.051* | |
H45 | −0.130 (4) | 0.288 (3) | 0.290 (10) | 0.051* | |
H46 | −0.026 (4) | 0.308 (2) | 0.359 (9) | 0.051* | |
Geometric parameters (Å, º) top
C1—C2 | 1.39 (2) | C14—N20 | 1.38 (2) |
C1—C6 | 1.41 (2) | C15—C16 | 1.38 (2) |
C1—H33 | 0.96 (7) | C15—H38 | 0.95 (8) |
C2—C3 | 1.43 (2) | C16—C17 | 1.42 (2) |
C2—H34 | 1.00 (7) | C16—H39 | 0.95 (8) |
C3—C4 | 1.39 (2) | C17—C18 | 1.43 (2) |
C3—H35 | 1.00 (7) | C17—N27 | 1.42 (2) |
C4—C5 | 1.42 (2) | C18—C19 | 1.38 (2) |
C4—H36 | 0.96 (7) | C18—H40 | 0.95 (7) |
C5—C6 | 1.40 (2) | C19—H41 | 0.95 (8) |
C5—N7 | 1.40 (2) | N20—C21 | 1.43 (2) |
C6—C8 | 1.43 (2) | C21—C22 | 1.42 (2) |
N7—C9 | 1.39 (2) | C21—C26 | 1.40 (2) |
N7—H32 | 0.82 (7) | C22—C23 | 1.39 (2) |
C8—C9 | 1.42 (2) | C22—H42 | 0.97 (8) |
C8—N10 | 1.39 (2) | C23—C24 | 1.41 (2) |
C9—C11 | 1.43 (2) | C23—H43 | 1.00 (8) |
N10—C12 | 1.34 (2) | C24—C25 | 1.41 (2) |
C11—C13 | 1.37 (2) | C24—H44 | 1.00 (8) |
C11—H37 | 0.94 (7) | C25—C26 | 1.40 (2) |
C12—C13 | 1.44 (2) | C25—H45 | 0.99 (7) |
C12—N20 | 1.45 (2) | C26—H46 | 0.97 (7) |
C13—C30 | 1.43 (2) | N27—O28 | 1.23 (1) |
C14—C15 | 1.45 (2) | N27—O29 | 1.25 (2) |
C14—C19 | 1.45 (2) | C30—N31 | 1.17 (1) |
| | | |
C6—C1—H33 | 115 (4) | C14—C15—H38 | 116 (5) |
C2—C1—H33 | 128 (4) | C14—C15—C16 | 120 (1) |
C2—C1—C6 | 117 (1) | C16—C15—H38 | 124 (5) |
C1—C2—H34 | 119 (4) | C15—C16—H39 | 121 (5) |
C1—C2—C3 | 121 (1) | C15—C16—C17 | 120 (1) |
C3—C2—H34 | 120 (4) | C17—C16—H39 | 119 (5) |
C2—C3—H35 | 120 (4) | C16—C17—N27 | 120 (1) |
C2—C3—C4 | 122 (1) | C16—C17—C18 | 121 (1) |
C4—C3—H35 | 118 (4) | C18—C17—N27 | 120 (1) |
C3—C4—H36 | 128 (4) | C17—C18—H40 | 118 (5) |
C3—C4—C5 | 117 (1) | C17—C18—C19 | 119 (1) |
C5—C4—H36 | 115 (4) | C19—C18—H40 | 122 (5) |
C4—C5—N7 | 128 (1) | C14—C19—C18 | 121 (1) |
C4—C5—C6 | 121 (1) | C18—C19—H41 | 124 (5) |
C6—C5—N7 | 111 (1) | C14—C19—H41 | 116 (4) |
C1—C6—C5 | 122 (1) | C12—N20—C14 | 118 (1) |
C5—C6—C8 | 106 (1) | C14—N20—C21 | 124 (1) |
C1—C6—C8 | 132 (1) | C12—N20—C21 | 114 (1) |
C5—N7—H32 | 126 (5) | N20—C21—C26 | 123 (1) |
C5—N7—C9 | 106 (1) | N20—C21—C22 | 118 (1) |
C9—N7—H32 | 128 (5) | C22—C21—C26 | 119 (1) |
C6—C8—N10 | 131 (1) | C21—C22—H42 | 114 (4) |
C6—C8—C9 | 107 (1) | C21—C22—C23 | 120 (1) |
C9—C8—N10 | 122 (1) | C23—C22—H42 | 126 (5) |
N7—C9—C8 | 110 (1) | C22—C23—H43 | 118 (5) |
C8—C9—C11 | 120 (1) | C22—C23—C24 | 120 (1) |
N7—C9—C11 | 130 (1) | C24—C23—H43 | 122 (4) |
C8—N10—C12 | 117 (1) | C23—C24—H44 | 120 (5) |
C9—C11—H37 | 119 (4) | C23—C24—C25 | 120 (1) |
C9—C11—C13 | 116 (1) | C25—C24—H44 | 120 (4) |
C13—C11—H37 | 125 (4) | C24—C25—H45 | 121 (4) |
N10—C12—N20 | 120 (1) | C24—C25—C26 | 120 (1) |
N10—C12—C13 | 122 (1) | C26—C25—H45 | 119 (5) |
C13—C12—N20 | 117 (1) | C21—C26—C25 | 121 (1) |
C11—C13—C12 | 122 (1) | C25—C26—H46 | 125 (4) |
C12—C13—C30 | 116 (1) | C21—C26—H46 | 115 (4) |
C11—C13—C30 | 121 (1) | C17—N27—O29 | 121 (1) |
C19—C14—N20 | 122 (1) | C17—N27—O28 | 123 (1) |
C15—C14—N20 | 119 (1) | O28—N27—O29 | 115 (1) |
C15—C14—C19 | 119 (1) | C13—C30—N31 | 174 (1) |
| | | |
C16—C17—N27—O28 | 13 (2) | C13—C12—N20—C14 | −125 (1) |
C9—C11—C13—C30 | 172 (1) | C12—N20—C21—C22 | 46 (2) |
C13—C12—N20—C21 | 77 (1) | C12—N20—C14—C15 | 27 (2) |
Experimental details
| (I) | (II) |
Crystal data |
Chemical formula | C24H15N5O2 | C24H15N5O2 |
Mr | 405.41 | 405.41 |
Crystal system, space group | Monoclinic, P21/n | Orthorhombic, Pbca |
Temperature (K) | 295 | 295 |
a, b, c (Å) | 16.131 (7), 18.070 (8), 14.349 (6) | 22.466 (8), 24.859 (9), 6.906 (3) |
α, β, γ (°) | 90, 91.95 (2), 90 | 90, 90, 90 |
V (Å3) | 4180 (3) | 3857 (3) |
Z | 8 | 8 |
Radiation type | Cu Kα1, λ = 1.54059 Å | Cu Kα1, λ = 1.54059 Å |
µ (mm−1) | 0.70 | 0.76 |
Specimen shape, size (mm) | Flat_sheet, 7 × 7 | Flat_sheet, 7 × 7 |
|
Data collection |
Diffractometer | Enraf-Nonius Guinier Johannson camera FR 552 diffractometer | Enraf-Nonius Guinier Johannson camera FR 552 diffractometer |
Specimen mounting | Pressed as a thin layer in the specimen holder of the camera | Pressed as a thin layer in the specimen holder of the camera |
Data collection mode | Transmission | Transmission |
Scan method | Stationary detector | Stationary detector |
2θ values (°) | 2θfixed = ? | 2θfixed = ? |
|
Refinement |
R factors and goodness of fit | Rp = 0.060, Rwp = 0.084, Rexp = 0.034, χ2 = 6.250 | Rp = 0.060, Rwp = 0.082, Rexp = 0.030, χ2 = 7.398 |
No. of data points | 7101 | 7501 |
No. of parameters | 312 | 179 |
No. of restraints | 315 | 151 |
H-atom treatment | H atoms treated by a mixture of independent and constrained refinement | H atoms treated by a mixture of independent and constrained refinement |
Hydrogen-bond geometry (Å, º) for (I) top
D—H···A | D—H | H···A | D···A | D—H···A |
N7A—H32A···N20Bi | .86 (18) | 2.16 (18) | 2.99 (3) | 162 (16) |
N7B—H32B···N20Aii | .86 (17) | 2.15 (17) | 2.99 (3) | 166 (16) |
Symmetry codes: (i) x+1/2, −y+1/2, z−1/2; (ii) x−1/2, −y+1/2, z−1/2. |
As has recently been demonstrated (Ryabova et al., 2001) the title compound, (I), irreversibly transforms into a new isomer with distinct properties after heating up the temperature higher than 603 K, or after the boiling in the solution of DMF in the presence of ButOK. Ryabova et al. (2001) assumed that this distinction in properties of two isomers can be explained by transformation of (I) into (II), which is unexpected and not the obvious one. Moreover, the NMR and mass-spectra data allow two possible molecular structures, (I) and (II), for the new isomer. In the cases where several isomers are indistinguishable by spectroscopic methods the crystal structure solution can help to determine a correct molecular structure even from laboratory powder data (Masciocchi et al., 1998; Chernyshev, Yatsenko et al., 1998; Chernyshev, Fitch et al., 1999; Chernyshev, Yatsenko et al., 1999). Therefore, the X-ray powder diffraction study was carried out. \sch
The monoclinic crystal structure of (I) contains two independent molecules, A and B (Fig.1), in the asymmetric unit. The molecules A and B are connected into chains via hydrogen bonds NH···N between the imino H atoms and azomethyne N atoms of adjacent molecules (Fig. 2, Table 1). The conformations of the molecules A and B are slightly different. The torsional angles C16A–C17A–N27A–O28A and C16B–C17B–N27B–O28B are equal, 3(3) and -19 (3)°, respectively. The phenyl planes from the nitrophenyl groups are inclined to the planes of tricyclic fragments at 85.6 (5) and 91.2 (6)° for A and B, respectively. The almost planar geometry of the nitrophenyl groups and the absence of conjugation between the electronic pairs of N10A and N10B and the attached phenyl rings, due to their perpendicularity to the tricyclic fragments, decreases π–electron density at the atoms C14A and C14B. The torsional angles C13A–C12A–N20A–C21A and C13B–C12B–N20B–C21B are equal 28 (4) and -3(4)°, respectively. It means that the lone pair of N20A atom is situated near the plane formed by atoms C14A, N10A, C12A and N20A, that assist the interaction between this lone pair and π-deficit atom C14A. The same situation is valid for the molecule B. It is possible to say that space geometry of A and B molecules is favourable for the reaction of isomerization, which results in compound (II). The exocyclic double bond C═N disappears in the molecule (II) (Fig.3), that causes the formation of thermodynamically more stable pyridinium cycle and the irreversibility of this isomerization.