2,3,4,9-Tetra­hydro-1H-carbazole

S Murugavel; P S Kannan; A SubbiahPandi; T Surendiran; S Balasubramanian

doi:10.1107/S1600536808038713

. 2008 Nov 26;64(Pt 12):o2433. doi: 10.1107/S1600536808038713

2,3,4,9-Tetrahydro-1H-carbazole

S Murugavel ^a, P S Kannan ^b, A SubbiahPandi ^c,^*, T Surendiran ^d, S Balasubramanian ^e

PMCID: PMC2960078 PMID: 21581401

Abstract

In the title compound, C₁₂H₁₃N, two methylene C atoms of the cyclohexene ring are disordered over two sites with occupancies of 0.591 (10) and 0.409 (10); both disorder components adopt half-chair conformations. The crystal structure is stabilized by intermolecular N—H⋯π and C—H⋯π interactions.

Related literature

For a related structure, see: Arulmozhi et al. (2008 ▶). For general background, see: Mi et al. (2003 ▶); Hewlins et al. (1984 ▶); Mohanakrishnan & Srinivasan (1995a ▶,b ▶); Kansal & Potier (1986 ▶); Phillipson & Zenk (1980 ▶); Saxton (1983 ▶); Abraham (1975 ▶).

Experimental

Crystal data

C₁₂H₁₃N
M _r = 171.23
Orthorhombic,
a = 6.1067 (4) Å
b = 7.9488 (5) Å
c = 19.4512 (12) Å
V = 944.18 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.07 mm⁻¹
T = 293 (2) K
0.26 × 0.15 × 0.15 mm

Data collection

Bruker Kappa APEXII area-detector diffractometer
Absorption correction: none
13269 measured reflections
1777 independent reflections
1323 reflections with I > 2σ(I)
R _int = 0.036

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.123
S = 1.07
1777 reflections
137 parameters
15 restraints
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.20 e Å⁻³

Data collection: APEX2 (Bruker, 2004 ▶); cell refinement: SAINT (Bruker, 2004 ▶); data reduction: SAINT; 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, 2003 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808038713/ci2708sup1.cif

e-64-o2433-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808038713/ci2708Isup2.hkl

e-64-o2433-Isup2.hkl^{(87.6KB, hkl)}

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—H1A⋯Cg2ⁱ	0.86	2.62	3.327 (1)	140
C4—H4⋯Cg1ⁱ	0.93	2.86	3.645 (1)	143
C12—H12B⋯Cg2ⁱⁱ	0.97	2.83	3.577 (2)	135
C12—H12D⋯Cg2ⁱⁱ	0.96	2.72	3.577 (2)	149

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Symmetry codes: (i) Inline graphic ; (ii) .Cg1 and Cg2 are the centroids of the N1/C5–C8 and C1–C6 rings, respectively.

Acknowledgments

The authors are grateful to Dr J. Jothi Kumar, Principal of Presidency College (Autonomous), Chennai, for providing computer and internet facilities. Dr Babu Vargheese, SAIF, IIT-Madras, India, is thanked for his help with the data collection.

supplementary crystallographic information

Comment

Carbazole derivatives exhibit good charge transfer and hole transporting properties, which are being explored for a multitude of optoelectronic and photocatalytic applications, including organic light emitting diodes (OLEDs) (Mi et al., 2003). In carbazole derivatives, the preliminary study shows that the presence of oxygenated substituents increases their biological activity (Hewlins et al., 1984). The 2,3-disubstituted indoles have been used as bidentate synthons for the synthesis of various medicinally important carbazole alkaloids (Mohanakrishnan & Srinivasan, 1995a,b). Intercalation between the base pairs in DNA has been implicated for their anticancer activity. It was conceived that the benzo[b] carbazoles as isosteric analogs of pyrido[4,3-b]carbazoles, with oxygenated D-ring could mimic the anti-cancer activity of ellipticine. So it was of interest to study the anticancer activity of D-ring oxygenated benzo[b]carbazoles as it is believed that these molecules could form a stable intercalation complex with DNA (Kansal & Potier, 1986). Tetrahydrocarbazole derivatives are present in the framework of indole-type alkaloids of biological interest (Phillipson & Zenk, 1980; Saxton, 1983; Abraham, 1975). We report here the crystal structure of the title compound (Fig. 1).

Bond lengths are normal and are comparable to the corresponding values observed in 1-naphthyl-9H-carbazole-4-sulfonate (Arulmozhi et al., 2008). The dihedral angle between the C1–C6 and N1/C5—C8 rings is 0.6 (1)°. Both the major and minor conformers of the disordered cyclohexene ring adopt half-chair conformations.

The crystal structure is stabilized by intermolecular N—H···π and C–H···π interactions (Table 1).

Experimental

A mixture of cyclohexanone (0.12 mol) and glacial acetic acid (40 ml) was heated and then redistilled phenylhydrazine (0.1 mol) was added dropwise for 30 min. The mixture was refluxed on a water bath for a further period of 30 min. The reaction mixture was poured into ice-cold water with continuous stirring and brown-coloured solid separated out. It was filtered, washed repeatedly with water and recrystallized from methanol in the presence of a little decolorized carbon to give the title compound. Single crystals suitable for X-ray diffraction were obtained by slow evaporation of a methanol solution.