Download citation
Download citation
link to html
The evidence for thermal isomerization of the title compound, C24H15N5O2, into 2-[(4-nitro­phenyl)­phenyl­amino]-5H-pyrido[3,2-b]­indole-3-carbo­nitrile has been obtained as a consequence of crystal structure determinations from laboratory powder data.

Supporting information

cif

Crystallographic Information File (CIF) https://doi.org/10.1107/S0108270101008356/br1336sup1.cif
Contains datablocks I, II, global

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108270101008356/br1336Isup2.rtv
Contains datablock I

rtv

Rietveld powder data file (CIF format) https://doi.org/10.1107/S0108270101008356/br1336IIsup3.rtv
Contains datablock II

CCDC references: 170207; 170208

Comment top

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 CN disappears in the molecule (II) (Fig.3), that causes the formation of thermodynamically more stable pyridinium cycle and the irreversibility of this isomerization.

Related literature top

For related literature, see: Chernyshev & Schenk (1998); Chernyshev, Fitch, Sonneveld, Kurbakov, Makarov & Tafeenko (1999); Chernyshev, Yatsenko, Tafeenko, Sonneveld & Schenk (1999); Chernyshev, Yatsenko, Tafeenko, Zhukov, Aslanov, Sonneveld, Schenk, Makarov, Granik, Trounov & Kurbakov (1998); Dollase (1986); Masciocchi et al. (1998); Ryabova et al. (2001); Stewart (1990); Visser (1969, 1986).

Experimental top

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).

Refinement top

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.

Computing details top

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).

Figures top
[Figure 1] Fig. 1. The two independent molecules of (I) with the atomic numbering.
[Figure 2] Fig. 2. The hydrogen bonds in (I).
[Figure 3] Fig. 3. The molecular structure of (II) with the atomic numbering.
[Figure 4] Fig. 4. The Rietveld plots, showing the observed and difference profiles for (I) (a) and (II) (b). The reflection positions are shown above the difference profile.
(I) 1-(4-Nitrophenyl)-2-phenylimino-2,5-dihydro-1H-pyrido[3,2-b]indole-3- carbonitrile top
Crystal data top
C24H15N5O2F(000) = 1680
Mr = 405.41Dx = 1.288 Mg m3
Monoclinic, P21/nMelting point = 478–479 K
a = 16.131 (7) ÅCu Kα1 radiation, λ = 1.54059 Å
b = 18.070 (8) ŵ = 0.70 mm1
c = 14.349 (6) ÅT = 295 K
β = 91.95 (2)°Particle morphology: parallelepiped
V = 4180 (3) Å3red
Z = 8flat_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 3502.223Data collection mode: transmission
Quartz monochromatorScan method: Stationary detector
Refinement top
Refinement on InetProfile function: split-type pseudo-Voigt (Toraya, 1986)
Least-squares matrix: full with fixed elements per cycle312 parameters
Rp = 0.060315 restraints
Rwp = 0.0840 constraints
Rexp = 0.034H atoms treated by a mixture of independent and constrained refinement
χ2 = 6.250Weighting scheme based on measured s.u.'s
7101 data points(Δ/σ)max = 0.025
Excluded region(s): 4.00 - 5.99Background function: Chebyshev polynomial up to the 5th order
Crystal data top
C24H15N5O2V = 4180 (3) Å3
Mr = 405.41Z = 8
Monoclinic, P21/nCu Kα1 radiation, λ = 1.54059 Å
a = 16.131 (7) ŵ = 0.70 mm1
b = 18.070 (8) ÅT = 295 K
c = 14.349 (6) Åflat_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 cameraScan method: Stationary detector
Refinement top
Rp = 0.0607101 data points
Rwp = 0.084312 parameters
Rexp = 0.034315 restraints
χ2 = 6.250H 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
xyzUiso*/Ueq
C1A0.6297 (17)0.3683 (15)0.1053 (16)0.051*
C2A0.5794 (15)0.3154 (14)0.152 (2)0.051*
C3A0.5954 (16)0.2936 (15)0.243 (2)0.051*
C4A0.6635 (17)0.3232 (15)0.2894 (17)0.051*
C5A0.7130 (16)0.3759 (14)0.2424 (19)0.051*
C6A0.6971 (17)0.3983 (14)0.151 (2)0.051*
N7A0.7807 (14)0.4125 (12)0.2717 (15)0.051*
C8A0.7577 (16)0.4506 (14)0.125 (2)0.051*
C9A0.8081 (16)0.4582 (13)0.202 (2)0.051*
N10A0.7725 (13)0.4911 (13)0.0446 (16)0.051*
C11A0.8760 (16)0.5058 (16)0.1996 (19)0.051*
C12A0.8390 (17)0.5400 (15)0.040 (2)0.051*
C13A0.8910 (17)0.5474 (14)0.118 (2)0.051*
C14A0.7271 (16)0.4795 (15)0.033 (2)0.051*
C15A0.6613 (18)0.5270 (15)0.053 (2)0.051*
C16A0.6166 (17)0.5167 (16)0.135 (2)0.051*
C17A0.6359 (15)0.4588 (14)0.1993 (19)0.051*
C18A0.7042 (17)0.4115 (15)0.180 (2)0.051*
C19A0.7489 (16)0.4231 (15)0.098 (2)0.051*
N20A0.8560 (13)0.5674 (12)0.0406 (16)0.051*
C21A0.9040 (16)0.6298 (15)0.055 (2)0.051*
C22A0.8840 (15)0.6995 (16)0.0180 (19)0.051*
C23A0.9348 (18)0.7613 (15)0.038 (2)0.051*
C24A1.0061 (16)0.7534 (14)0.096 (2)0.051*
C25A1.0261 (16)0.6836 (15)0.1333 (19)0.051*
C26A0.9741 (17)0.6223 (14)0.114 (2)0.051*
N27A0.5909 (13)0.4512 (12)0.2852 (17)0.051*
O28A0.5345 (11)0.4958 (9)0.2931 (11)0.051*
O29A0.6165 (12)0.4034 (11)0.3378 (16)0.051*
C30A0.9694 (15)0.5758 (13)0.1063 (18)0.051*
N31A1.0373 (11)0.5918 (9)0.0848 (13)0.051*
H32A0.802 (10)0.408 (9)0.325 (12)0.051*
H33A0.618 (10)0.383 (9)0.045 (11)0.051*
H34A0.534 (10)0.296 (9)0.122 (11)0.051*
H35A0.562 (9)0.259 (9)0.273 (12)0.051*
H36A0.675 (10)0.309 (9)0.350 (12)0.051*
H37A0.910 (9)0.510 (9)0.251 (12)0.051*
H38A0.647 (9)0.564 (9)0.011 (12)0.051*
H39A0.573 (10)0.549 (9)0.144 (12)0.051*
H40A0.720 (10)0.373 (8)0.220 (12)0.051*
H41A0.792 (9)0.392 (9)0.084 (12)0.051*
H42A0.837 (9)0.706 (9)0.021 (12)0.051*
H43A0.922 (10)0.807 (8)0.012 (13)0.051*
H44A1.040 (10)0.794 (9)0.109 (13)0.051*
H45A1.073 (9)0.678 (9)0.172 (12)0.051*
H46A0.987 (10)0.577 (8)0.141 (11)0.051*
C1B0.1664 (17)0.1714 (16)0.09440 (18)0.051*
C2B0.1224 (16)0.2285 (13)0.1406 (2)0.051*
C3B0.1303 (16)0.2408 (14)0.2365 (2)0.051*
C4B0.1822 (17)0.1949 (14)0.28810 (18)0.051*
C5B0.2251 (15)0.1377 (14)0.2412 (2)0.051*
C6B0.2177 (15)0.1251 (14)0.1455 (2)0.051*
N7B0.2778 (14)0.0869 (12)0.27540 (15)0.051*
C8B0.2687 (17)0.0645 (14)0.1212 (2)0.051*
C9B0.3044 (16)0.0422 (15)0.2039 (2)0.051*
N10B0.2868 (14)0.0282 (12)0.03850 (16)0.051*
C11B0.3593 (16)0.0172 (16)0.20630 (19)0.051*
C12B0.3407 (17)0.0314 (15)0.0379 (2)0.051*
C13B0.3783 (17)0.0539 (14)0.1217 (2)0.051*
C14B0.2568 (15)0.0564 (15)0.0430 (2)0.051*
C15B0.1815 (17)0.0294 (15)0.0752 (2)0.051*
C16B0.1515 (16)0.0581 (16)0.1591 (2)0.051*
C17B0.1963 (17)0.1092 (14)0.2168 (2)0.051*
C18B0.2730 (17)0.1374 (13)0.1840 (2)0.051*
C19B0.3024 (17)0.1077 (15)0.0988 (2)0.051*
N20B0.3497 (12)0.0668 (11)0.03920 (15)0.051*
C21B0.4004 (17)0.1281 (15)0.0478 (2)0.051*
C22B0.3749 (15)0.1994 (15)0.0216 (2)0.051*
C23B0.4292 (18)0.2600 (14)0.0337 (2)0.051*
C24B0.5083 (16)0.2498 (14)0.0755 (2)0.051*
C25B0.5341 (17)0.1786 (14)0.1020 (2)0.051*
C26B0.4794 (17)0.1181 (14)0.0897 (2)0.051*
N27B0.1602 (12)0.1334 (11)0.30420 (15)0.051*
O28B0.1059 (12)0.0918 (11)0.33100 (16)0.051*
O29B0.1890 (17)0.1882 (15)0.34140 (15)0.051*
C30B0.4553 (13)0.0930 (13)0.12580 (15)0.051*
N31B0.5142 (11)0.1273 (10)0.14430 (12)0.051*
H32B0.292 (10)0.083 (9)0.3325 (12)0.051*
H33B0.161 (10)0.164 (10)0.0307 (11)0.051*
H34B0.088 (10)0.259 (10)0.1069 (12)0.051*
H35B0.100 (10)0.278 (8)0.2660 (12)0.051*
H36B0.187 (10)0.202 (9)0.3519 (12)0.051*
H37B0.382 (9)0.030 (9)0.2628 (12)0.051*
H38B0.152 (10)0.004 (9)0.0387 (12)0.051*
H39B0.101 (9)0.037 (9)0.1763 (12)0.051*
H40B0.307 (11)0.171 (9)0.2177 (13)0.051*
H41B0.352 (9)0.125 (9)0.0768 (12)0.051*
H42B0.322 (9)0.207 (8)0.0048 (12)0.051*
H43B0.412 (10)0.307 (8)0.0150 (13)0.051*
H44B0.544 (9)0.290 (9)0.0833 (12)0.051*
H45B0.586 (9)0.171 (9)0.1298 (12)0.051*
H46B0.497 (11)0.071 (8)0.1091 (12)0.051*
Geometric parameters (Å, º) top
C1A—C2A1.41 (4)C1B—C2B1.41 (4)
C1A—C6A1.40 (4)C1B—C6B1.40 (4)
C1A—H33A0.93 (16)C1B—H33B0.93 (16)
C2A—C3A1.40 (4)C2B—C3B1.40 (4)
C2A—H34A0.93 (16)C2B—H34B0.93 (17)
C3A—C4A1.41 (4)C3B—C4B1.41 (4)
C3A—H35A0.93 (15)C3B—H35B0.93 (16)
C4A—C5A1.40 (4)C4B—C5B1.40 (4)
C4A—H36A0.93 (17)C4B—H36B0.93 (17)
C5A—C6A1.40 (4)C5B—C6B1.40 (4)
C5A—N7A1.36 (3)C5B—N7B1.35 (3)
C6A—C8A1.40 (4)C6B—C8B1.41 (4)
N7A—C9A1.36 (3)N7B—C9B1.36 (4)
N7A—H32A0.86 (18)N7B—H32B0.86 (17)
C8A—C9A1.40 (4)C8B—C9B1.40 (4)
C8A—N10A1.38 (4)C8B—N10B1.38 (4)
C9A—C11A1.39 (4)C9B—C11B1.39 (4)
N10A—C12A1.39 (4)N10B—C12B1.38 (4)
N10A—C14A1.37 (4)N10B—C14B1.38 (4)
C11A—C13A1.41 (4)C11B—C13B1.41 (4)
C11A—H37A0.93 (17)C11B—H37B0.93 (18)
C12A—C13A1.42 (4)C12B—C13B1.42 (4)
C12A—N20A1.28 (4)C12B—N20B1.28 (4)
C13A—C30A1.37 (4)C13B—C30B1.43 (3)
C14A—C15A1.40 (4)C14B—C15B1.40 (4)
C14A—C19A1.41 (4)C14B—C19B1.41 (4)
C15A—C16A1.41 (4)C15B—C16B1.41 (4)
C15A—H38A0.93 (17)C15B—H38B0.93 (16)
C16A—C17A1.43 (4)C16B—C17B1.42 (4)
C16A—H39A0.93 (16)C16B—H39B0.94 (16)
C17A—C18A1.43 (4)C17B—C18B1.43 (4)
C17A—N27A1.46 (4)C17B—N27B1.47 (4)
C18A—C19A1.42 (4)C18B—C19B1.43 (4)
C18A—H40A0.93 (16)C18B—H40B0.93 (17)
C19A—H41A0.93 (16)C19B—H41B0.93 (15)
N20A—C21A1.38 (3)N20B—C21B1.38 (3)
C21A—C22A1.40 (4)C21B—C22B1.40 (4)
C21A—C26A1.40 (4)C21B—C26B1.40 (4)
C22A—C23A1.41 (4)C22B—C23B1.41 (4)
C22A—H42A0.93 (16)C22B—H42B0.93 (15)
C23A—C24A1.40 (4)C23B—C24B1.40 (4)
C23A—H43A0.93 (16)C23B—H43B0.93 (15)
C24A—C25A1.40 (4)C24B—C25B1.40 (4)
C24A—H44A0.93 (16)C24B—H44B0.93 (15)
C25A—C26A1.41 (4)C25B—C26B1.41 (4)
C25A—H45A0.93 (15)C25B—H45B0.93 (15)
C26A—H46A0.93 (15)C26B—H46B0.93 (15)
N27A—O28A1.22 (3)N27B—O28B1.23 (3)
N27A—O29A1.21 (3)N27B—O29B1.21 (3)
C30A—N31A1.16 (3)C30B—N31B1.17 (3)
C6A—C1A—H33A120 (10)C6B—C1B—H33B120 (10)
C2A—C1A—H33A121 (10)C2B—C1B—H33B120 (10)
C2A—C1A—C6A119 (2)C2B—C1B—C6B119 (2)
C1A—C2A—H34A120 (10)C1B—C2B—H34B120 (10)
C1A—C2A—C3A121 (2)C1B—C2B—C3B121 (3)
C3A—C2A—H34A120 (10)C3B—C2B—H34B119 (10)
C2A—C3A—H35A120 (11)C2B—C3B—H35B120 (10)
C2A—C3A—C4A120 (3)C2B—C3B—C4B120 (3)
C4A—C3A—H35A120 (9)C4B—C3B—H35B120 (10)
C3A—C4A—H36A121 (11)C3B—C4B—H36B121 (10)
C3A—C4A—C5A118 (2)C3B—C4B—C5B118 (2)
C5A—C4A—H36A121 (10)C5B—C4B—H36B121 (10)
C4A—C5A—N7A129 (2)C4B—C5B—N7B129 (2)
C4A—C5A—C6A121 (2)C4B—C5B—C6B122 (2)
C6A—C5A—N7A109 (2)C6B—C5B—N7B109 (2)
C1A—C6A—C5A120 (3)C1B—C6B—C5B119 (2)
C5A—C6A—C8A107 (2)C5B—C6B—C8B108 (2)
C1A—C6A—C8A133 (3)C1B—C6B—C8B133 (2)
C5A—N7A—H32A126 (12)C5B—N7B—H32B126 (11)
C5A—N7A—C9A108 (2)C5B—N7B—C9B108 (2)
C9A—N7A—H32A126 (12)C9B—N7B—H32B125 (11)
C6A—C8A—N10A133 (3)C6B—C8B—N10B134 (3)
C6A—C8A—C9A106 (2)C6B—C8B—C9B106 (2)
C9A—C8A—N10A121 (3)C9B—C8B—N10B121 (3)
N7A—C9A—C8A110 (2)N7B—C9B—C8B110 (2)
C8A—C9A—C11A122 (2)C8B—C9B—C11B122 (2)
N7A—C9A—C11A129 (2)N7B—C9B—C11B128 (3)
C8A—N10A—C14A121 (2)C8B—N10B—C14B119 (2)
C8A—N10A—C12A119 (2)C8B—N10B—C12B119 (2)
C12A—N10A—C14A119 (2)C12B—N10B—C14B121 (2)
C9A—C11A—H37A121 (10)C9B—C11B—H37B119 (10)
C9A—C11A—C13A117 (2)C9B—C11B—C13B118 (2)
C13A—C11A—H37A122 (11)C13B—C11B—H37B123 (11)
N10A—C12A—N20A116 (2)N10B—C12B—N20B117 (2)
N10A—C12A—C13A120 (2)N10B—C12B—C13B120 (2)
C13A—C12A—N20A124 (3)C13B—C12B—N20B123 (3)
C11A—C13A—C12A121 (3)C11B—C13B—C12B120 (3)
C12A—C13A—C30A121 (2)C12B—C13B—C30B125 (2)
C11A—C13A—C30A116 (2)C11B—C13B—C30B111 (2)
N10A—C14A—C19A121 (3)N10B—C14B—C19B122 (3)
N10A—C14A—C15A120 (2)N10B—C14B—C15B119 (2)
C15A—C14A—C19A119 (2)C15B—C14B—C19B119 (2)
C14A—C15A—H38A119 (10)C14B—C15B—H38B119 (10)
C14A—C15A—C16A120 (3)C14B—C15B—C16B119 (2)
C16A—C15A—H38A121 (11)C16B—C15B—H38B122 (11)
C15A—C16A—H39A117 (10)C15B—C16B—H39B114 (10)
C15A—C16A—C17A122 (3)C15B—C16B—C17B124 (3)
C17A—C16A—H39A121 (10)C17B—C16B—H39B122 (10)
C16A—C17A—N27A121 (2)C16B—C17B—N27B119 (2)
C16A—C17A—C18A118 (2)C16B—C17B—C18B118 (2)
C18A—C17A—N27A121 (2)C18B—C17B—N27B123 (2)
C17A—C18A—H40A122 (10)C17B—C18B—H40B123 (11)
C17A—C18A—C19A119 (2)C17B—C18B—C19B118 (2)
C19A—C18A—H40A119 (11)C19B—C18B—H40B119 (11)
C14A—C19A—C18A122 (3)C14B—C19B—C18B123 (3)
C18A—C19A—H41A119 (10)C18B—C19B—H41B119 (10)
C14A—C19A—H41A119 (10)C14B—C19B—H41B118 (10)
C12A—N20A—C21A123 (2)C12B—N20B—C21B122 (2)
N20A—C21A—C26A117 (2)N20B—C21B—C26B118 (2)
N20A—C21A—C22A124 (2)N20B—C21B—C22B123 (2)
C22A—C21A—C26A119 (2)C22B—C21B—C26B119 (2)
C21A—C22A—H42A120 (10)C21B—C22B—H42B120 (10)
C21A—C22A—C23A121 (3)C21B—C22B—C23B120 (2)
C23A—C22A—H42A119 (10)C23B—C22B—H42B119 (10)
C22A—C23A—H43A120 (10)C22B—C23B—H43B120 (10)
C22A—C23A—C24A120 (3)C22B—C23B—C24B120 (2)
C24A—C23A—H43A120 (11)C24B—C23B—H43B120 (10)
C23A—C24A—H44A120 (10)C23B—C24B—H44B120 (10)
C23A—C24A—C25A119 (2)C23B—C24B—C25B120 (2)
C25A—C24A—H44A120 (10)C25B—C24B—H44B120 (10)
C24A—C25A—H45A120 (10)C24B—C25B—H45B120 (10)
C24A—C25A—C26A120 (2)C24B—C25B—C26B120 (2)
C26A—C25A—H45A120 (10)C26B—C25B—H45B120 (10)
C21A—C26A—C25A120 (2)C21B—C26B—C25B121 (2)
C25A—C26A—H46A119 (9)C25B—C26B—H46B119 (9)
C21A—C26A—H46A120 (10)C21B—C26B—H46B120 (10)
C17A—N27A—O29A115 (2)C17B—N27B—O29B118 (2)
C17A—N27A—O28A114 (2)C17B—N27B—O28B113 (2)
O28A—N27A—O29A131 (2)O28B—N27B—O29B129 (2)
C13A—C30A—N31A169 (3)C13B—C30B—N31B169 (2)
C16A—C17A—N27A—O28A3 (3)C16B—C17B—N27B—O28B19 (3)
C8A—N10A—C14A—C15A100 (3)C8B—N10B—C14B—C15B94 (3)
C9A—C11A—C13A—C30A161 (2)C9B—C11B—C13B—C30B158 (2)
C13A—C12A—N20A—C21A28 (4)C13B—C12B—N20B—C21B3 (4)
C12A—N20A—C21A—C22A61 (4)C12B—N20B—C21B—C22B83 (3)
Hydrogen-bond geometry (Å, º) top
D—H···AD—HH···AD···AD—H···A
N7A—H32A···N20Bi0.86 (18)2.16 (18)2.99 (3)162 (16)
N7B—H32B···N20Aii0.86 (17)2.15 (17)2.99 (3)166 (16)
Symmetry codes: (i) x+1/2, y+1/2, z1/2; (ii) x1/2, y+1/2, z1/2.
(II) 2-[(4-Nitrophenyl)-phenylamino]-5H-pyrido[3,2-b]indole-3-carbonitrile top
Crystal data top
C24H15N5O2Dx = 1.396 Mg m3
Mr = 405.41Melting point = 600–602 K
Orthorhombic, PbcaCu Kα1 radiation, λ = 1.54059 Å
a = 22.466 (8) ŵ = 0.76 mm1
b = 24.859 (9) ÅT = 295 K
c = 6.906 (3) ÅParticle morphology: needles
V = 3857 (3) Å3Yellow
Z = 8flat_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 3502.223Data collection mode: transmission
Quartz monochromatorScan method: Stationary detector
Refinement top
Refinement on Inet179 parameters
Least-squares matrix: full with fixed elements per cycle151 restraints
Rp = 0.06030 constraints
Rwp = 0.082H atoms treated by a mixture of independent and constrained refinement
Rexp = 0.030Weighting scheme based on measured s.u.'s
χ2 = 7.398(Δ/σ)max = 0.02
7501 data pointsBackground function: Chebyshev polynomial up to the 5th order
Excluded region(s): 4.00 - 4.99Preferred orientation correction: March-Dollase (Dollase, 1986)
Profile function: split-type pseudo-Voigt (Toraya, 1986)
Crystal data top
C24H15N5O2V = 3857 (3) Å3
Mr = 405.41Z = 8
Orthorhombic, PbcaCu Kα1 radiation, λ = 1.54059 Å
a = 22.466 (8) ŵ = 0.76 mm1
b = 24.859 (9) ÅT = 295 K
c = 6.906 (3) Åflat_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 cameraScan method: Stationary detector
Refinement top
Rp = 0.0607501 data points
Rwp = 0.082179 parameters
Rexp = 0.030151 restraints
χ2 = 7.398H 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
xyzUiso*/Ueq
C10.1759 (7)0.4555 (4)0.475 (2)0.081 (4)*
C20.2033 (7)0.4880 (6)0.6117 (15)0.081 (4)*
C30.2024 (7)0.5452 (6)0.5948 (15)0.081 (4)*
C40.1734 (7)0.5710 (5)0.4437 (17)0.081 (4)*
C50.1453 (7)0.5377 (6)0.3033 (17)0.081 (4)*
C60.1472 (7)0.4815 (5)0.3190 (16)0.081 (4)*
N70.1143 (6)0.5535 (4)0.1367 (15)0.081 (4)*
C80.1152 (7)0.4612 (6)0.1552 (15)0.081 (4)*
C90.0953 (7)0.5064 (5)0.0477 (16)0.081 (4)*
N100.1019 (6)0.4088 (4)0.0983 (11)0.081 (4)*
C110.0621 (7)0.4992 (6)0.1273 (15)0.081 (4)*
C120.0707 (7)0.4024 (5)0.0662 (15)0.081 (4)*
C130.0500 (7)0.4471 (5)0.1792 (15)0.081 (4)*
C140.1000 (6)0.3121 (6)0.1645 (14)0.081 (4)*
C150.1586 (7)0.3314 (5)0.2156 (16)0.081 (4)*
C160.2037 (7)0.2957 (6)0.2571 (15)0.081 (4)*
C170.1926 (7)0.2394 (5)0.2510 (17)0.081 (4)*
C180.1351 (6)0.2191 (5)0.1979 (17)0.081 (4)*
C190.0900 (6)0.2547 (5)0.1543 (15)0.081 (4)*
N200.0548 (6)0.3489 (4)0.1327 (13)0.081 (4)*
C210.0054 (7)0.3342 (4)0.0910 (16)0.081 (4)*
C220.0275 (8)0.3449 (6)0.0985 (16)0.081 (4)*
C230.0867 (7)0.3344 (6)0.1429 (14)0.081 (4)*
C240.1251 (6)0.3130 (6)0.0016 (17)0.081 (4)*
C250.1039 (7)0.3038 (5)0.1877 (16)0.081 (4)*
C260.0442 (6)0.3135 (6)0.2315 (16)0.081 (4)*
N270.2392 (5)0.2029 (4)0.2941 (14)0.081 (4)*
O280.2863 (4)0.2167 (3)0.3701 (9)0.081 (4)*
O290.2349 (4)0.1541 (7)0.2553 (10)0.081 (4)*
C300.0241 (5)0.4343 (4)0.3628 (15)0.081 (4)*
N310.0020 (5)0.4256 (3)0.5065 (13)0.081 (4)*
H320.109 (4)0.585 (3)0.101 (9)0.051*
H330.174 (4)0.417 (3)0.473 (9)0.051*
H340.224 (4)0.471 (3)0.723 (9)0.051*
H350.222 (4)0.568 (3)0.696 (9)0.051*
H360.170 (4)0.609 (3)0.420 (10)0.051*
H370.050 (4)0.530 (3)0.197 (9)0.051*
H380.163 (4)0.369 (3)0.219 (9)0.051*
H390.243 (4)0.308 (3)0.291 (10)0.051*
H400.130 (4)0.181 (3)0.193 (10)0.051*
H410.051 (4)0.244 (3)0.121 (9)0.051*
H420.002 (4)0.360 (3)0.186 (9)0.051*
H430.101 (4)0.342 (3)0.278 (11)0.051*
H440.168 (4)0.307 (3)0.032 (10)0.051*
H450.130 (4)0.288 (3)0.290 (10)0.051*
H460.026 (4)0.308 (2)0.359 (9)0.051*
Geometric parameters (Å, º) top
C1—C21.39 (2)C14—N201.38 (2)
C1—C61.41 (2)C15—C161.38 (2)
C1—H330.96 (7)C15—H380.95 (8)
C2—C31.43 (2)C16—C171.42 (2)
C2—H341.00 (7)C16—H390.95 (8)
C3—C41.39 (2)C17—C181.43 (2)
C3—H351.00 (7)C17—N271.42 (2)
C4—C51.42 (2)C18—C191.38 (2)
C4—H360.96 (7)C18—H400.95 (7)
C5—C61.40 (2)C19—H410.95 (8)
C5—N71.40 (2)N20—C211.43 (2)
C6—C81.43 (2)C21—C221.42 (2)
N7—C91.39 (2)C21—C261.40 (2)
N7—H320.82 (7)C22—C231.39 (2)
C8—C91.42 (2)C22—H420.97 (8)
C8—N101.39 (2)C23—C241.41 (2)
C9—C111.43 (2)C23—H431.00 (8)
N10—C121.34 (2)C24—C251.41 (2)
C11—C131.37 (2)C24—H441.00 (8)
C11—H370.94 (7)C25—C261.40 (2)
C12—C131.44 (2)C25—H450.99 (7)
C12—N201.45 (2)C26—H460.97 (7)
C13—C301.43 (2)N27—O281.23 (1)
C14—C151.45 (2)N27—O291.25 (2)
C14—C191.45 (2)C30—N311.17 (1)
C6—C1—H33115 (4)C14—C15—H38116 (5)
C2—C1—H33128 (4)C14—C15—C16120 (1)
C2—C1—C6117 (1)C16—C15—H38124 (5)
C1—C2—H34119 (4)C15—C16—H39121 (5)
C1—C2—C3121 (1)C15—C16—C17120 (1)
C3—C2—H34120 (4)C17—C16—H39119 (5)
C2—C3—H35120 (4)C16—C17—N27120 (1)
C2—C3—C4122 (1)C16—C17—C18121 (1)
C4—C3—H35118 (4)C18—C17—N27120 (1)
C3—C4—H36128 (4)C17—C18—H40118 (5)
C3—C4—C5117 (1)C17—C18—C19119 (1)
C5—C4—H36115 (4)C19—C18—H40122 (5)
C4—C5—N7128 (1)C14—C19—C18121 (1)
C4—C5—C6121 (1)C18—C19—H41124 (5)
C6—C5—N7111 (1)C14—C19—H41116 (4)
C1—C6—C5122 (1)C12—N20—C14118 (1)
C5—C6—C8106 (1)C14—N20—C21124 (1)
C1—C6—C8132 (1)C12—N20—C21114 (1)
C5—N7—H32126 (5)N20—C21—C26123 (1)
C5—N7—C9106 (1)N20—C21—C22118 (1)
C9—N7—H32128 (5)C22—C21—C26119 (1)
C6—C8—N10131 (1)C21—C22—H42114 (4)
C6—C8—C9107 (1)C21—C22—C23120 (1)
C9—C8—N10122 (1)C23—C22—H42126 (5)
N7—C9—C8110 (1)C22—C23—H43118 (5)
C8—C9—C11120 (1)C22—C23—C24120 (1)
N7—C9—C11130 (1)C24—C23—H43122 (4)
C8—N10—C12117 (1)C23—C24—H44120 (5)
C9—C11—H37119 (4)C23—C24—C25120 (1)
C9—C11—C13116 (1)C25—C24—H44120 (4)
C13—C11—H37125 (4)C24—C25—H45121 (4)
N10—C12—N20120 (1)C24—C25—C26120 (1)
N10—C12—C13122 (1)C26—C25—H45119 (5)
C13—C12—N20117 (1)C21—C26—C25121 (1)
C11—C13—C12122 (1)C25—C26—H46125 (4)
C12—C13—C30116 (1)C21—C26—H46115 (4)
C11—C13—C30121 (1)C17—N27—O29121 (1)
C19—C14—N20122 (1)C17—N27—O28123 (1)
C15—C14—N20119 (1)O28—N27—O29115 (1)
C15—C14—C19119 (1)C13—C30—N31174 (1)
C16—C17—N27—O2813 (2)C13—C12—N20—C14125 (1)
C9—C11—C13—C30172 (1)C12—N20—C21—C2246 (2)
C13—C12—N20—C2177 (1)C12—N20—C14—C1527 (2)

Experimental details

(I)(II)
Crystal data
Chemical formulaC24H15N5O2C24H15N5O2
Mr405.41405.41
Crystal system, space groupMonoclinic, P21/nOrthorhombic, Pbca
Temperature (K)295295
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), 9090, 90, 90
V3)4180 (3)3857 (3)
Z88
Radiation typeCu Kα1, λ = 1.54059 ÅCu Kα1, λ = 1.54059 Å
µ (mm1)0.700.76
Specimen shape, size (mm)Flat_sheet, 7 × 7Flat_sheet, 7 × 7
Data collection
DiffractometerEnraf-Nonius Guinier Johannson camera FR 552
diffractometer
Enraf-Nonius Guinier Johannson camera FR 552
diffractometer
Specimen mountingPressed as a thin layer in the specimen holder of the cameraPressed as a thin layer in the specimen holder of the camera
Data collection modeTransmissionTransmission
Scan methodStationary detectorStationary detector
2θ values (°)2θfixed = ?2θfixed = ?
Refinement
R factors and goodness of fitRp = 0.060, Rwp = 0.084, Rexp = 0.034, χ2 = 6.250Rp = 0.060, Rwp = 0.082, Rexp = 0.030, χ2 = 7.398
No. of data points71017501
No. of parameters312179
No. of restraints315151
H-atom treatmentH atoms treated by a mixture of independent and constrained refinementH atoms treated by a mixture of independent and constrained refinement

Computer programs: Johannson LS18 linescanner data collection program, LSPAID (Visser et al., 1986), Philips Profile Fit 1.0b (Philips, 1996), MRIA (Chernyshev & Zlokazov, 1992), PLUTON (Spek, 1992), MRIA, SHELXL93 (Sheldrick, 1993) and PARST (Nardelli, 1983).

Hydrogen-bond geometry (Å, º) for (I) top
D—H···AD—HH···AD···AD—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, z1/2; (ii) x1/2, y+1/2, z1/2.
 

Follow Acta Cryst. C
Sign up for e-alerts
Follow Acta Cryst. on Twitter
Follow us on facebook
Sign up for RSS feeds