3-Methyl-3,4-dihydro-9H-carbazol-1(2H)-one

A Thomas Gunaseelan; K Prabakaran; K J Rajendra Prasad; A Thiruvalluvar; R J Butcher

doi:10.1107/S1600536809028050

. 2009 Jul 22;65(Pt 8):o1946–o1947. doi: 10.1107/S1600536809028050

3-Methyl-3,4-dihydro-9H-carbazol-1(2H)-one

A Thomas Gunaseelan ^a, K Prabakaran ^b, K J Rajendra Prasad ^b, A Thiruvalluvar ^a,^*, R J Butcher ^c

PMCID: PMC2977477 PMID: 21583627

Abstract

In the title molecule, C₁₃H₁₃NO, the dihedral angle between the benzene ring and the fused pyrrole ring is 2.03 (5)°. The methyl group at the 3-position has an equatorial orientation. The cyclohexene ring adopts an envelope conformation. Three C atoms of the cyclohexene ring, with their attached H atoms, and all atoms of the methyl group are disordered over two positions, the site-occupancy factors being 0.883 (2) and 0.117 (2). In the crystal structure, molecules are stabilized by intermolecular N—H⋯O hydrogen bonds. A C—H⋯π interaction, involving the benzene ring, is also found.

Related literature

For the biological activity of substituted 2,3,4,9-tetrahydrocarbazoles, see: Mooradian et al. (1977 ▶); Jean et al. (2004 ▶); Biere et al. (1973 ▶); Lacoume (1973 ▶). For carbazole alkaloids, such as clausenapin, murrayafoline-A, murrayafoline-B, murrayastine, murrayaquinone-A, with a methyl substituent at the C-3 position, see: Knolker & Reddy (2002 ▶). For the preparation of 1-oxo compounds via their corresponding hydrazones, see: Sowmithran & Rajendra Prasad (1986 ▶); Rajendra Prasad & Vijayalakshmi (1994 ▶); Gunaseelan et al. (2007a ▶,b ▶); Sridharan et al. (2008 ▶); Thiruvalluvar et al. (2007 ▶).

Experimental

Crystal data

C₁₃H₁₃NO
M _r = 199.24
Triclinic,
a = 5.8301 (3) Å
b = 8.4348 (5) Å
c = 10.8000 (7) Å
α = 78.094 (5)°
β = 75.942 (5)°
γ = 87.166 (5)°
V = 504.11 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.08 mm⁻¹
T = 110 K
0.54 × 0.14 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur Ruby diffractometer
Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009 ▶) T _min = 0.753, T _max = 1.000 (expected range = 0.747–0.992)
5927 measured reflections
3292 independent reflections
2400 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.153
S = 1.00
3292 reflections
144 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.27 e Å⁻³

Data collection: CrysAlis Pro (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis Pro; data reduction: CrysAlis Pro; 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: PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809028050/wn2337sup1.cif

e-65-o1946-sup1.cif^{(23.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809028050/wn2337Isup2.hkl

e-65-o1946-Isup2.hkl^{(158.2KB, 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
N9—H9⋯O1ⁱ	0.960 (17)	1.939 (16)	2.848 (1)	157.2 (13)
C4A—H4B⋯Cg1ⁱⁱ	0.99	2.83	3.779 (1)	162

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Symmetry codes: (i) Inline graphic ; (ii) . Cg1 is the centroid of the C4D,C5–C8,C8A ring.

Acknowledgments

RJB acknowledges the NSF MRI program (grant No. CHE-0619278) for funds to purchase an X-ray diffractometer.

supplementary crystallographic information

Comment

Substituted 2,3,4,9-tetrahydrocarbazoles have been reported to possess many biological properties, such as central nervous system activity (Mooradian et al., 1977), antihistamine (Jean et al., 2004), antidiabetic (Biere et al., 1973) and anti-inflammatory properties (Lacoume, 1973). We have attached importance to the title compound since some of the carbazole alkaloids, such as clausenapin, murrayafoline-A, murrayafoline-B, murrayastine, murrayaquinone-A have the methyl group as substituent at the C-3 position (Knolker & Reddy, 2002). The preparation of 1-oxo compounds via their corresponding hydrazones have been reported (Sowmithran & Rajendra Prasad, 1986; Rajendra Prasad & Vijayalakshmi, 1994). Guanaseelan et al. (2007a,b), Thiruvalluvar et al. (2007) and Sridharan et al. (2008) have reported the crystal structures of substituted carbazole derivatives, in which the carbazole units are not planar.

In the title molecule, C₁₃H₁₃NO, the dihedral angle between the benzene ring and the fused pyrrole ring is 2.03 (5)°. The methyl group at position 3 has an equatorial oreintation. The cyclohexene ring adopts an envelope conformation. In the crystal structure, the molecules are stabilized by intermolecular N9—H9···O1(-1 - x, 1 - y, 1 - z) hydrogen bonds. Furthermore, a C4A—H4B···π(-x, -y, 1 - z) interaction, involving the benzene ring(C4D—C8A), is also found in the crystal stucture.

Experimental

A solution of 2-(2-phenylhydrazono)-5-methylcyclohexanone (0.216 g. 0.001 mol) in a mixture of acetic acid (20 ml) and hydrochloric acid (5 ml) was refluxed on an oil bath pre-heated to 398 K for 2 h. The contents were then cooled and poured into cold water with stirring. The brown solid which was separated by passing through a column of silica gel and eluted with a (98:2, v/v) petroleum ether-ethyl acetate mixture to yield the title compound (0.148 g, 74%). This was recrystallized from ethanol.