2-(6-Chloro-2,3,4,9-tetra­hydro-1H-carbazol-1-yl­idene)propane­dinitrile

M Sekar; R Velmurugan; A V Vijayasankar; P Ramesh; M N Ponnuswamy

doi:10.1107/S1600536811046575

. 2011 Nov 12;67(Pt 12):o3268. doi: 10.1107/S1600536811046575

2-(6-Chloro-2,3,4,9-tetrahydro-1H-carbazol-1-ylidene)propanedinitrile

M Sekar ^a, R Velmurugan ^a, A V Vijayasankar ^b, P Ramesh ^c, M N Ponnuswamy ^c,^*

PMCID: PMC3238926 PMID: 22199775

Abstract

The molecular conformation of the title compound, C₁₅H₁₀ClN₃, is stabilized by an intramolecular N—H⋯N hydrogen bond with an S(7) ring motif. The crystal packing is controlled by N—H⋯N and C—H⋯N intermolecular interactions. One of the methylene groups of the cyclohexene ring is disordered over two positions with refined occupancies of 0.457 (12) and 0.543 (12).

Related literature

For the biological activity of carbazole derivatives, see: Shufen et al. (1995 ▶); Magnus et al. (1992 ▶); Abraham (1975 ▶); Saxton (1983 ▶); Phillipson & Zenk (1980 ▶); Kirtikar & Basu (1933 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₅H₁₀ClN₃
M _r = 267.71
Monoclinic,
a = 7.5731 (3) Å
b = 7.6865 (3) Å
c = 22.2867 (8) Å
β = 97.437 (2)°
V = 1286.41 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 293 K
0.20 × 0.19 × 0.17 mm

Data collection

Bruker SMART APEX CCD detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T _min = 0.945, T _max = 0.953
24123 measured reflections
3828 independent reflections
2569 reflections with I > 2σ(I)
R _int = 0.031

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.164
S = 1.01
3828 reflections
186 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT-Plus (Bruker, 1998 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97 and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811046575/bt5656sup1.cif

e-67-o3268-sup1.cif^{(24.2KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811046575/bt5656Isup2.hkl

e-67-o3268-Isup2.hkl^{(187.7KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811046575/bt5656Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯N16	0.94 (3)	2.60 (3)	3.373 (2)	139.5 (19)
N1—H1⋯N16ⁱ	0.94 (3)	2.27 (3)	3.099 (3)	147 (2)
C11—H11⋯N18ⁱⁱ	0.93	2.48	3.352 (3)	156

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

The authors thank Indian Institute of Science, Bangalore, India, for the data collection.

supplementary crystallographic information

Comment

Carbazole alkaloids obtained from natural sources have been the subject of extensive research, mainly because of their widespread applications in traditional medicine (Kirtikar & Basu, 1933). Aminocarbazoles are widely used as intermediates for the preparation of carbazole-based synthetic dyes, agrochemicals, pharmaceuticals, light-sensitive materials (Shufen et al., 1995). Tetrahydrocarbazole systems are present in the framework of a number of indole-type alkaloids of biological interest (Magnus et al., 1992; Abraham, 1975; Saxton, 1983; Phillipson et al., 1980). Against this background and to ascertain the molecular structure and conformation, the crystal structure determination of the title compound has been carried out.

The ORTEP plot of the molecule is shown in Fig. 1. One of the C atoms of the cyclohexene ring is disordered with refined occupancies of 0.457 (12) and 0.543 (12). The sum of the bond angles around N1 [359.8°] is in accordance with sp² hybridization. The bond lengths (C15—N16) 1.145 (3)Å & (C17—N18) 1.144 (3)Å and the bond angles, (C14—C15—N16) 176.9 (2)° & (C14—C17—N18) 178.6 (3)° show linear character of the cyano group, a feature observed in carbonitrile compounds.

The crystal packing reveals that symmetry-related molecules are linked through a network by C—H···N, N—H···N and π···π types of intra and intermolecular interactions. The intramolecular N1—H1···N16 hydrogen bond generates a S(7) ring motif. The molecules at (x, y, z) and (-x - 1, -y - 1, -z) are linked by N1—H1···N16 hydrogen bonds into cyclic centrosymmetric R₂²(14) dimer. The dimers are linked via inter molecular C11—H11···N18 hydrogen bond, which forms a one dimensional chain running along diagonally in ac-disection.

Experimental

A mixture of 6-Chloro-1-oxo-1,2,3,4-tetrahydrocarbazole (7.5 mmol), and melanonitrile (7.5 mmol), ammonium acetate (0.57 g, 8.125 mmol) and acetic acid (1.5 ml, 24.75 mmol) in 12.5 ml of toluene was stirred at 105°C for 5 h. On cooling the precipitate that formed was filtered off, washed with hexane (20 ml) and dried at 100°C to give a crude product of 6-chloro-2-(1,2,3,4- tetrahydro-9H-carbazol-1-ylidene)propanedinitrile.The crystals of the title compound suitable for single XRD analysis were obtained by the slow evaporation method by using dichloroethane as solvent at room temperature.