6-Methyl-2,3,4,9-tetra­hydro-1H-carbazole-1-thione

R Archana; K Prabakaran; K J Rajendra Prasad; A Thiruvalluvar; R J Butcher

doi:10.1107/S1600536811019246

. 2011 Jun 11;67(Pt 7):o1642. doi: 10.1107/S1600536811019246

6-Methyl-2,3,4,9-tetrahydro-1H-carbazole-1-thione

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

PMCID: PMC3151814 PMID: 21837047

Abstract

In the title molecule, C₁₃H₁₃NS, the dihedral angle between the benzene ring and the fused pyrrole ring is 0.71 (8)° and the cyclohexene ring is in an envelope form. The (CH₂)₃ atoms of the cyclohexene ring are disordered over two positions; the site-occupancy factor for the major component refined to 0.862 (4). In the crystal, intermolecular N—H⋯S hydrogen bonds lead to the formation of centrosymmetric aggregates via an R ₂ ²(10) ring.

Related literature

For the synthesis of fused carbazole nuclei, see: Pelly et al. (2005 ▶). For heterocycle-annulated tetra-, penta- and hexacyclic carbazole derivatives, see: Chattopadhyay et al. (2006 ▶). For the preparation of 1-oxo compounds via their corresponding hydrazones, see: Rajendra Prasad & Vijayalakshmi (1994 ▶). For related structures, see: Archana et al. (2010 ▶); Thomas Gunaseelan et al. (2009 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₃H₁₃NS
M _r = 215.31
Triclinic,
a = 7.0846 (4) Å
b = 9.5287 (7) Å
c = 9.6384 (6) Å
α = 115.009 (7)°
β = 104.901 (6)°
γ = 98.074 (6)°
V = 546.28 (8) Å³
Z = 2
Cu Kα radiation
μ = 2.31 mm⁻¹
T = 295 K
0.46 × 0.28 × 0.21 mm

Data collection

Oxford Diffraction Xcalibur Ruby Gemini diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.609, T _max = 1.000
3471 measured reflections
2102 independent reflections
1924 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.133
S = 1.06
2102 reflections
145 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); 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 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811019246/tk2746sup1.cif

e-67-o1642-sup1.cif^{(18.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811019246/tk2746Isup2.hkl

e-67-o1642-Isup2.hkl^{(101.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811019246/tk2746Isup3.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
N9—H9⋯S1ⁱ	0.86 (2)	2.77 (3)	3.4955 (15)	143 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

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

supplementary crystallographic information

Comment

The development of methods for the synthesis of fused carbazole nuclei is becoming increasingly important as a result of the number of natural and synthetic carbazoles that display biological activity (Pelly et al., 2005). Heterocycle-annulated tetra-, penta- and hexa-cyclic carbazole derivatives have been developed using successive applications of three atom economic processes, viz., Claisen rearrangement, olefin metathesis and Diels-Alder reactions (Chattopadhyay et al., 2006). The preparation of 1-oxo compounds via their corresponding hydrazones has been reported (Rajendra Prasad & Vijayalakshmi, 1994). Archana et al. (2010) and Thomas Gunaseelan et al. (2009) have reported the crystal structures of substituted carbazole derivatives, in which the carbazole units are not planar.

In the title molecule, Fig. 1, the dihedral angle between the benzene ring and the fused pyrrole ring is 0.71 (8) °. The cyclohexene ring is in envelope form. Three C atoms (C2A, C3A, C4A) of the cyclohexene ring, with their attached H atoms are disordered over two positions; the site-occupancy factors are ca 0.86 and 0.14. Intermolecular N—H···S hydrogen bonds form a R²₂(10) (Bernstein et al., 1995) ring in the crystal structure (Table 1 & Fig. 2).

Experimental

A mixture of 6-methyl-2,3,4,9-tetrahydro-1H-carbazol-1-one (0.199 g, 0.001 mol) and Lawesson's reagent (0.404 g, 0.001 mol) was refluxed in pyridine on an oil bath pre-heated to 383 K for 6 h. The contents were poured onto cold water and neutralized using 1:1 HCl, filtered and dried. The product was recrystallized from ethanol. The yield was 0.154 g (72%).