6-Methyl-2,3,4,9-tetra-hydro-1H-carbazole-1-thione.

In the title mol-ecule, C(13)H(13)NS, the dihedral angle between the benzene ring and the fused pyrrole ring is 0.71 (8)° and the cyclo-hexene ring is in an envelope form. The (CH(2))(3) atoms of the cyclo-hexene ring are disordered over two positions; the site-occupancy factor for the major component refined to 0.862 (4). In the crystal, inter-molecular 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 = 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

Δρmax = 0.33 e Å−3

Δρmin = −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.

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

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

Supplementary material file. DOI: 10.1107/S1600536811019246/tk2746Isup3.cml

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

C13H13NS	Z = 2
Mr = 215.31	F(000) = 228
Triclinic, P1	Dx = 1.309 Mg m−3
Hall symbol: -P 1	Melting point: 356 K
a = 7.0846 (4) Å	Cu Kα radiation, λ = 1.54184 Å
b = 9.5287 (7) Å	Cell parameters from 2595 reflections
c = 9.6384 (6) Å	θ = 5.3–72.6°
α = 115.009 (7)°	µ = 2.31 mm−1
β = 104.901 (6)°	T = 295 K
γ = 98.074 (6)°	Chunk, orange
V = 546.28 (8) Å3	0.46 × 0.28 × 0.21 mm

Oxford Diffraction Xcalibur Ruby Gemini diffractometer	2102 independent reflections
Radiation source: Enhance (Cu) X-ray Source	1924 reflections with I > 2σ(I)
graphite	Rint = 0.022
Detector resolution: 10.5081 pixels mm-1	θmax = 72.8°, θmin = 5.3°
ω scans	h = −7→8
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010)	k = −11→11
Tmin = 0.609, Tmax = 1.000	l = −9→11
3471 measured reflections

Refinement on F2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F2 > 2σ(F2)] = 0.045	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.133	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0834P)2 + 0.089P] where P = (Fo2 + 2Fc2)/3
2102 reflections	(Δ/σ)max = 0.001
145 parameters	Δρmax = 0.33 e Å−3
3 restraints	Δρmin = −0.22 e Å−3

Geometry. Bond distances, angles etc. have been calculated using the rounded fractional coordinates. All su's are estimated from the variances of the (full) variance-covariance matrix. The cell e.s.d.'s are taken into account in the estimation of distances, angles and torsion angles

Refinement. Refinement of F2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F2, conventional R-factors R are based on F, with F set to zero for negative F2. The threshold expression of F2 > 2σ(F2) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F2 are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

	x	y	z	Uiso*/Ueq	Occ. (<1)
S1	1.12016 (7)	0.28362 (5)	0.07548 (6)	0.0567 (1)
N9	0.79545 (19)	0.08614 (14)	0.14611 (15)	0.0412 (3)
C1	0.9615 (3)	0.34787 (18)	0.16910 (19)	0.0438 (4)
C2A	0.9571 (3)	0.5227 (2)	0.2371 (3)	0.0611 (6)	0.862 (4)
C3A	0.7579 (4)	0.5495 (2)	0.2548 (3)	0.0590 (7)	0.862 (4)
C4A	0.6807 (3)	0.47256 (19)	0.3468 (2)	0.0531 (5)	0.862 (4)
C4C	0.6904 (3)	0.30147 (17)	0.27848 (18)	0.0421 (4)
C4D	0.5783 (2)	0.16637 (17)	0.27860 (17)	0.0396 (4)
C5	0.4231 (3)	0.14228 (19)	0.33927 (19)	0.0443 (4)
C6	0.3399 (2)	−0.00860 (19)	0.31681 (18)	0.0430 (4)
C7	0.4130 (2)	−0.13824 (18)	0.23121 (19)	0.0444 (4)
C8	0.5640 (2)	−0.12039 (18)	0.16959 (19)	0.0426 (4)
C8A	0.6473 (2)	0.03337 (17)	0.19299 (17)	0.0382 (4)
C9A	0.8222 (2)	0.24863 (17)	0.19625 (18)	0.0406 (4)
C16	0.1720 (3)	−0.0386 (2)	0.3790 (2)	0.0530 (5)
C4B	0.6807 (3)	0.47256 (19)	0.3468 (2)	0.0531 (5)	0.138 (4)
C3B	0.855 (2)	0.5809 (14)	0.3534 (18)	0.0590 (7)	0.138 (4)
C2B	0.9571 (3)	0.5227 (2)	0.2371 (3)	0.0611 (6)	0.138 (4)
H3A	0.65603	0.50556	0.14672	0.0708*	0.862 (4)
H2B	0.98737	0.56293	0.16579	0.0733*	0.862 (4)
H4B	0.54131	0.47484	0.33584	0.0637*	0.862 (4)
H3B	0.77491	0.66471	0.31193	0.0708*	0.862 (4)
H4A	0.76376	0.53281	0.46218	0.0637*	0.862 (4)
H8	0.60931	−0.20752	0.11426	0.0512*
H9	0.856 (3)	0.029 (3)	0.086 (2)	0.050 (5)*
H16A	0.14149	0.06091	0.43500	0.0795*
H16B	0.21516	−0.08010	0.45319	0.0795*
H16C	0.05241	−0.11568	0.28852	0.0795*
H5	0.37662	0.22852	0.39473	0.0531*
H7	0.35612	−0.24001	0.21612	0.0532*
H2A	1.06434	0.58601	0.34358	0.0733*	0.862 (4)
H2C	1.09697	0.59042	0.28888	0.0733*	0.138 (4)
H2D	0.89345	0.53906	0.14537	0.0733*	0.138 (4)
H3C	0.80970	0.66932	0.34463	0.0708*	0.138 (4)
H3D	0.95675	0.62673	0.46174	0.0708*	0.138 (4)
H4C	0.55597	0.47686	0.27954	0.0637*	0.138 (4)
H4D	0.67683	0.50937	0.45626	0.0637*	0.138 (4)

	U11	U22	U33	U12	U13	U23
S1	0.0577 (2)	0.0544 (2)	0.0691 (3)	0.0166 (2)	0.0349 (2)	0.0319 (2)
N9	0.0486 (6)	0.0350 (6)	0.0475 (6)	0.0156 (5)	0.0246 (5)	0.0209 (5)
C1	0.0476 (8)	0.0392 (7)	0.0458 (7)	0.0084 (6)	0.0155 (6)	0.0232 (6)
C2A	0.0759 (11)	0.0386 (8)	0.0776 (11)	0.0143 (8)	0.0367 (9)	0.0307 (7)
C3A	0.0760 (14)	0.0372 (8)	0.0728 (13)	0.0214 (9)	0.0301 (11)	0.0304 (9)
C4A	0.0659 (10)	0.0342 (7)	0.0616 (9)	0.0190 (7)	0.0300 (8)	0.0194 (6)
C4C	0.0506 (8)	0.0340 (7)	0.0432 (7)	0.0125 (6)	0.0184 (6)	0.0187 (5)
C4D	0.0474 (7)	0.0338 (6)	0.0402 (6)	0.0132 (5)	0.0179 (6)	0.0180 (5)
C5	0.0517 (8)	0.0407 (7)	0.0453 (7)	0.0181 (6)	0.0239 (6)	0.0194 (6)
C6	0.0440 (7)	0.0451 (7)	0.0416 (7)	0.0113 (6)	0.0178 (6)	0.0211 (6)
C7	0.0493 (8)	0.0363 (7)	0.0497 (7)	0.0093 (6)	0.0188 (6)	0.0226 (6)
C8	0.0504 (8)	0.0342 (6)	0.0468 (7)	0.0147 (6)	0.0206 (6)	0.0197 (5)
C8A	0.0439 (7)	0.0347 (6)	0.0389 (6)	0.0132 (5)	0.0167 (5)	0.0183 (5)
C9A	0.0481 (8)	0.0339 (6)	0.0426 (7)	0.0119 (6)	0.0174 (6)	0.0200 (5)
C16	0.0521 (9)	0.0552 (9)	0.0545 (8)	0.0109 (7)	0.0256 (7)	0.0262 (7)
C4B	0.0659 (10)	0.0342 (7)	0.0616 (9)	0.0190 (7)	0.0300 (8)	0.0194 (6)
C3B	0.0760 (14)	0.0372 (8)	0.0728 (13)	0.0214 (9)	0.0301 (11)	0.0304 (9)
C2B	0.0759 (11)	0.0386 (8)	0.0776 (11)	0.0143 (8)	0.0367 (9)	0.0307 (7)

S1—C1	1.643 (2)	C7—C8	1.374 (2)
N9—C8A	1.359 (2)	C8—C8A	1.398 (3)
N9—C9A	1.380 (2)	C2A—H2A	0.9700
N9—H9	0.86 (2)	C2A—H2B	0.9700
C1—C9A	1.420 (3)	C2B—H2C	0.9700
C1—C2B	1.519 (3)	C2B—H2D	0.9700
C1—C2A	1.519 (3)	C3A—H3A	0.9700
C2A—C3A	1.508 (4)	C3A—H3B	0.9700
C2B—C3B	1.446 (15)	C3B—H3C	0.9700
C3A—C4A	1.520 (3)	C3B—H3D	0.9700
C3B—C4B	1.463 (15)	C4A—H4A	0.9700
C4A—C4C	1.498 (3)	C4A—H4B	0.9700
C4B—C4C	1.498 (3)	C4B—H4D	0.9700
C4C—C4D	1.415 (3)	C4B—H4C	0.9700
C4C—C9A	1.389 (3)	C5—H5	0.9300
C4D—C5	1.406 (3)	C7—H7	0.9300
C4D—C8A	1.422 (2)	C8—H8	0.9300
C5—C6	1.376 (3)	C16—H16C	0.9600
C6—C16	1.507 (3)	C16—H16A	0.9600
C6—C7	1.419 (2)	C16—H16B	0.9600
C8A—N9—C9A	108.73 (13)	H2A—C2A—H2B	108.00
C8A—N9—H9	127.5 (19)	C1—C2B—H2C	108.00
C9A—N9—H9	123.4 (19)	C1—C2B—H2D	108.00
S1—C1—C2B	121.48 (16)	C3B—C2B—H2C	108.00
C2A—C1—C9A	114.66 (17)	C3B—C2B—H2D	108.00
C2B—C1—C9A	114.66 (17)	H2C—C2B—H2D	107.00
S1—C1—C2A	121.48 (16)	C2A—C3A—H3B	109.00
S1—C1—C9A	123.85 (14)	C4A—C3A—H3A	109.00
C1—C2A—C3A	114.80 (19)	C2A—C3A—H3A	109.00
C1—C2B—C3B	118.3 (6)	H3A—C3A—H3B	108.00
C2A—C3A—C4A	113.5 (2)	C4A—C3A—H3B	109.00
C2B—C3B—C4B	121.0 (10)	C2B—C3B—H3D	107.00
C3A—C4A—C4C	109.36 (17)	C2B—C3B—H3C	107.00
C3B—C4B—C4C	112.2 (6)	C4B—C3B—H3D	107.00
C4B—C4C—C9A	122.29 (17)	H3C—C3B—H3D	107.00
C4B—C4C—C4D	130.69 (18)	C4B—C3B—H3C	107.00
C4A—C4C—C4D	130.69 (18)	C3A—C4A—H4A	110.00
C4A—C4C—C9A	122.29 (17)	C3A—C4A—H4B	110.00
C4D—C4C—C9A	107.01 (15)	H4A—C4A—H4B	108.00
C4C—C4D—C5	134.04 (17)	C4C—C4A—H4A	110.00
C4C—C4D—C8A	106.52 (14)	C4C—C4A—H4B	110.00
C5—C4D—C8A	119.43 (16)	C4C—C4B—H4D	109.00
C4D—C5—C6	120.16 (17)	H4C—C4B—H4D	108.00
C7—C6—C16	119.78 (17)	C3B—C4B—H4C	109.00
C5—C6—C16	121.41 (16)	C3B—C4B—H4D	109.00
C5—C6—C7	118.81 (16)	C4C—C4B—H4C	109.00
C6—C7—C8	123.03 (17)	C4D—C5—H5	120.00
C7—C8—C8A	117.67 (15)	C6—C5—H5	120.00
N9—C8A—C4D	108.52 (15)	C6—C7—H7	119.00
N9—C8A—C8	130.59 (15)	C8—C7—H7	118.00
C4D—C8A—C8	120.89 (14)	C7—C8—H8	121.00
N9—C9A—C4C	109.22 (15)	C8A—C8—H8	121.00
C1—C9A—C4C	124.73 (17)	C6—C16—H16A	109.00
N9—C9A—C1	126.04 (15)	C6—C16—H16B	109.00
C1—C2A—H2A	109.00	C6—C16—H16C	109.00
C1—C2A—H2B	109.00	H16A—C16—H16B	109.00
C3A—C2A—H2A	109.00	H16A—C16—H16C	109.00
C3A—C2A—H2B	109.00	H16B—C16—H16C	109.00
C9A—N9—C8A—C4D	−1.01 (16)	C4A—C4C—C9A—N9	−179.30 (14)
C9A—N9—C8A—C8	179.17 (15)	C4A—C4C—C9A—C1	0.7 (3)
C8A—N9—C9A—C1	−179.28 (15)	C4D—C4C—C9A—N9	−0.11 (17)
C8A—N9—C9A—C4C	0.70 (17)	C4D—C4C—C9A—C1	179.87 (15)
S1—C1—C2A—C3A	155.86 (17)	C4C—C4D—C5—C6	178.74 (17)
C9A—C1—C2A—C3A	−25.3 (3)	C8A—C4D—C5—C6	0.4 (2)
S1—C1—C9A—N9	−1.7 (2)	C4C—C4D—C8A—N9	0.93 (17)
S1—C1—C9A—C4C	178.38 (13)	C4C—C4D—C8A—C8	−179.22 (14)
C2A—C1—C9A—N9	179.56 (16)	C5—C4D—C8A—N9	179.65 (14)
C2A—C1—C9A—C4C	−0.4 (2)	C5—C4D—C8A—C8	−0.5 (2)
C1—C2A—C3A—C4A	51.1 (3)	C4D—C5—C6—C7	−0.3 (2)
C2A—C3A—C4A—C4C	−48.2 (2)	C4D—C5—C6—C16	−179.42 (15)
C3A—C4A—C4C—C4D	−155.34 (19)	C5—C6—C7—C8	0.2 (2)
C3A—C4A—C4C—C9A	23.7 (2)	C16—C6—C7—C8	179.32 (15)
C4A—C4C—C4D—C5	0.2 (3)	C6—C7—C8—C8A	−0.2 (2)
C4A—C4C—C4D—C8A	178.61 (16)	C7—C8—C8A—N9	−179.81 (15)
C9A—C4C—C4D—C5	−178.95 (17)	C7—C8—C8A—C4D	0.4 (2)
C9A—C4C—C4D—C8A	−0.50 (17)

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)

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)

Symmetry code: (i) .