2-Amino-6-methyl-4,5,6,7-tetra-hydro-1-benzothio-phene-3-carbonitrile.

In the title compound, C(10)H(12)N(2)S, one of the C atoms of the cyclo-hexene ring (at position 6) and the methyl group attached to it are disordered over two sets of sites in a 0.650 (3):0.350 (3) ratio. The cyclo-hexene ring in both the major and minor occupancy conformers adopts a half-chair conformation. The thio-phene ring is essentially planar (r.m.s. deviation = 0.05 Å). In the crystal, N-H⋯N hydrogen bonds involving the amino groups result in inversion dimers with R(2) (2)(12) graph-set motif. Further N-H⋯N hydrogen bonds involving the amino and carbonitrile groups generate zigzag chains along the a axis.

Related literature

For preparation of the title compound, see: Shetty et al. (2009 ▶). For general background to benzothio­phenes, see: Katritzky et al. (1996 ▶); Shishoo & Jain (1992 ▶). For related structures, see: Akkurt et al. (2008 ▶); Harrison et al. (2006 ▶); Vasu et al. (2004 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C10H12N2S

M = 192.29

Monoclinic,

a = 9.0415 (2) Å

b = 8.3294 (2) Å

c = 13.1283 (3) Å

β = 90.169 (2)°

V = 988.69 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.28 mm−1

T = 123 K

0.16 × 0.16 × 0.14 mm

Data collection

Bruker SMART APEX CCD detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.957, T max = 0.962

11284 measured reflections

2441 independent reflections

1878 reflections with I > 2σ(I)

R int = 0.039

Refinement

R[F 2 > 2σ(F 2)] = 0.040

wR(F 2) = 0.107

S = 1.07

2441 reflections

127 parameters

H-atom parameters constrained

Δρmax = 0.39 e Å−3

Δρmin = −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: CAMERON (Watkin et al., 1996 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811006076/pv2384sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811006076/pv2384Isup2.hkl

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

C10H12N2S	F(000) = 408
Mr = 192.29	Dx = 1.292 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 2441 reflections
a = 9.0415 (2) Å	θ = 2.9–29.2°
b = 8.3294 (2) Å	µ = 0.28 mm−1
c = 13.1283 (3) Å	T = 123 K
β = 90.169 (2)°	Block, yellow
V = 988.69 (4) Å3	0.16 × 0.16 × 0.14 mm
Z = 4

Bruker SMART APEX CCD detector diffractometer	2441 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1878 reflections with I > 2σ(I)
graphite	Rint = 0.039
ω scans	θmax = 29.2°, θmin = 2.9°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −11→12
Tmin = 0.957, Tmax = 0.962	k = −11→10
11284 measured reflections	l = −17→16

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.0536P)2 + 0.2028P] where P = (Fo2 + 2Fc2)/3
2441 reflections	(Δ/σ)max = 0.001
127 parameters	Δρmax = 0.39 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

Experimental. The compound was synthesized by following the procedure given in NitinKumar et al., (2009)

Geometry. All s.u.'s (except the s.u. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell s.u.'s are taken into account individually in the estimation of s.u.'s in distances, angles and torsion angles; correlations between s.u.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell s.u.'s is used for estimating s.u.'s involving l.s. planes.

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	0.68698 (5)	0.02703 (5)	0.34885 (3)	0.02519 (15)
N1	0.5603 (2)	−0.40456 (18)	0.60740 (11)	0.0378 (4)
N2	0.54766 (17)	−0.25706 (17)	0.33230 (10)	0.0292 (4)
H2A	0.5129	−0.3480	0.3565	0.035*
H2B	0.5362	−0.2336	0.2674	0.035*
C1	0.5991 (2)	−0.3000 (2)	0.55684 (12)	0.0263 (4)
C2	0.64719 (19)	−0.16794 (19)	0.49726 (12)	0.0224 (4)
C3	0.61829 (18)	−0.15372 (19)	0.39455 (12)	0.0217 (3)
C4	0.75534 (19)	0.0810 (2)	0.46849 (12)	0.0251 (4)
C5	0.72696 (19)	−0.0328 (2)	0.53858 (12)	0.0236 (4)
C6	0.7762 (2)	−0.0180 (2)	0.64700 (13)	0.0303 (4)
H6A	0.8312	−0.1158	0.6670	0.036*
H6B	0.6885	−0.0088	0.6916	0.036*
C7	0.8734 (3)	0.1266 (3)	0.66129 (16)	0.0514 (6)
H7A	0.8688	0.1572	0.7341	0.062*	0.650 (3)
H7B	0.9764	0.0931	0.6474	0.062*	0.650 (3)
C8	0.8387 (2)	0.2343 (2)	0.48637 (13)	0.0328 (4)
H8A	0.7892	0.3236	0.4500	0.039*	0.650 (3)
H8B	0.9405	0.2241	0.4596	0.039*	0.650 (3)
C9A	0.8440 (3)	0.2705 (3)	0.6012 (2)	0.0296 (5)	0.650 (3)
H9AA	0.7434	0.3094	0.6209	0.036*	0.650 (3)
C10A	0.9518 (5)	0.4053 (5)	0.6248 (3)	0.0429 (10)	0.650 (3)
H10A	0.9544	0.4241	0.6985	0.064*	0.650 (3)
H10B	0.9199	0.5034	0.5900	0.064*	0.650 (3)
H10C	1.0508	0.3753	0.6013	0.064*	0.650 (3)
H7C	0.8128	0.2072	0.6977	0.062*	0.350 (3)
H7D	0.9527	0.0937	0.7091	0.062*	0.350 (3)
H8C	0.7690	0.3238	0.4988	0.039*	0.350 (3)
H8D	0.8997	0.2611	0.4262	0.039*	0.350 (3)
C9B	0.9414 (6)	0.2065 (6)	0.5837 (4)	0.0296 (5)	0.350 (3)
H9BA	1.0221	0.1334	0.5601	0.036*	0.350 (3)
C10B	1.0183 (9)	0.3644 (11)	0.6111 (7)	0.0429 (10)	0.350 (3)
H10D	0.9449	0.4508	0.6140	0.064*	0.350 (3)
H10E	1.0924	0.3897	0.5592	0.064*	0.350 (3)
H10F	1.0669	0.3537	0.6775	0.064*	0.350 (3)

	U11	U22	U33	U12	U13	U23
S1	0.0327 (3)	0.0257 (2)	0.0171 (2)	−0.00706 (18)	−0.00294 (16)	0.00388 (16)
N1	0.0684 (12)	0.0241 (8)	0.0207 (8)	−0.0089 (8)	−0.0066 (7)	0.0026 (6)
N2	0.0453 (9)	0.0247 (8)	0.0175 (7)	−0.0093 (7)	−0.0035 (6)	0.0003 (6)
C1	0.0395 (10)	0.0207 (8)	0.0187 (8)	−0.0005 (7)	−0.0035 (7)	−0.0027 (7)
C2	0.0287 (9)	0.0203 (8)	0.0183 (8)	0.0000 (7)	−0.0001 (6)	0.0010 (6)
C3	0.0241 (8)	0.0207 (8)	0.0203 (8)	−0.0003 (6)	0.0011 (6)	0.0004 (6)
C4	0.0296 (9)	0.0270 (9)	0.0185 (8)	−0.0053 (7)	−0.0033 (7)	0.0010 (7)
C5	0.0263 (9)	0.0243 (8)	0.0202 (8)	−0.0017 (7)	−0.0011 (7)	0.0004 (7)
C6	0.0427 (11)	0.0294 (9)	0.0189 (9)	−0.0041 (8)	−0.0057 (7)	0.0030 (7)
C7	0.0744 (17)	0.0471 (13)	0.0327 (11)	−0.0244 (12)	−0.0248 (11)	0.0067 (9)
C8	0.0418 (11)	0.0330 (10)	0.0237 (9)	−0.0159 (8)	−0.0040 (8)	0.0028 (7)
C9A	0.0321 (14)	0.0302 (13)	0.0265 (12)	−0.0074 (10)	−0.0027 (11)	−0.0028 (10)
C10A	0.047 (3)	0.052 (2)	0.0294 (16)	−0.029 (2)	−0.0007 (19)	−0.0052 (15)
C7A	0.0744 (17)	0.0471 (13)	0.0327 (11)	−0.0244 (12)	−0.0248 (11)	0.0067 (9)
C8A	0.0418 (11)	0.0330 (10)	0.0237 (9)	−0.0159 (8)	−0.0040 (8)	0.0028 (7)
C9B	0.0321 (14)	0.0302 (13)	0.0265 (12)	−0.0074 (10)	−0.0027 (11)	−0.0028 (10)
C10B	0.047 (3)	0.052 (2)	0.0294 (16)	−0.029 (2)	−0.0007 (19)	−0.0052 (15)

S1—C3	1.7363 (16)	C7—H7A	0.9900
S1—C4	1.7451 (17)	C7—H7B	0.9900
N1—C1	1.150 (2)	C8—C9A	1.538 (3)
N2—C3	1.347 (2)	C8—H8A	0.9900
N2—H2A	0.8800	C8—H8B	0.9900
N2—H2B	0.8800	C9A—C10A	1.519 (5)
C1—C2	1.419 (2)	C9A—H9AA	1.0000
C2—C3	1.378 (2)	C10A—H10A	0.9800
C2—C5	1.442 (2)	C10A—H10B	0.9800
C4—C5	1.346 (2)	C10A—H10C	0.9800
C4—C8	1.501 (2)	C9B—C10B	1.530 (10)
C5—C6	1.495 (2)	C9B—H9BA	1.0000
C6—C7	1.502 (3)	C10B—H10D	0.9800
C6—H6A	0.9900	C10B—H10E	0.9800
C6—H6B	0.9900	C10B—H10F	0.9800
C7—C9A	1.459 (3)
C3—S1—C4	92.20 (8)	C9A—C7—H7A	107.6
C3—N2—H2A	120.0	C6—C7—H7A	107.6
C3—N2—H2B	120.0	C9A—C7—H7B	107.6
H2A—N2—H2B	120.0	C6—C7—H7B	107.6
N1—C1—C2	178.19 (17)	H7A—C7—H7B	107.0
C3—C2—C1	123.28 (15)	C4—C8—C9A	109.52 (16)
C3—C2—C5	113.22 (14)	C4—C8—H8A	109.8
C1—C2—C5	123.47 (14)	C9A—C8—H8A	109.8
N2—C3—C2	128.84 (15)	C4—C8—H8B	109.8
N2—C3—S1	120.93 (12)	C9A—C8—H8B	109.8
C2—C3—S1	110.22 (12)	H8A—C8—H8B	108.2
C5—C4—C8	126.07 (15)	C7—C9A—C10A	112.4 (3)
C5—C4—S1	111.48 (13)	C7—C9A—C8	112.0 (2)
C8—C4—S1	122.42 (12)	C10A—C9A—C8	111.3 (2)
C4—C5—C2	112.86 (15)	C7—C9A—H9AA	106.9
C4—C5—C6	122.40 (15)	C10A—C9A—H9AA	106.9
C2—C5—C6	124.73 (15)	C8—C9A—H9AA	106.9
C5—C6—C7	110.93 (15)	C10B—C9B—H9BA	105.4
C5—C6—H6A	109.5	C9B—C10B—H10D	109.5
C7—C6—H6A	109.5	C9B—C10B—H10E	109.5
C5—C6—H6B	109.5	H10D—C10B—H10E	109.5
C7—C6—H6B	109.5	C9B—C10B—H10F	109.5
H6A—C6—H6B	108.0	H10D—C10B—H10F	109.5
C9A—C7—C6	119.06 (19)	H10E—C10B—H10F	109.5
C1—C2—C3—N2	−2.3 (3)	C1—C2—C5—C4	−177.32 (17)
C5—C2—C3—N2	179.55 (17)	C3—C2—C5—C6	−178.44 (17)
C1—C2—C3—S1	177.36 (14)	C1—C2—C5—C6	3.4 (3)
C5—C2—C3—S1	−0.78 (19)	C4—C5—C6—C7	−6.7 (3)
C4—S1—C3—N2	−179.86 (15)	C2—C5—C6—C7	172.46 (19)
C4—S1—C3—C2	0.45 (13)	C5—C6—C7—C9A	34.4 (3)
C3—S1—C4—C5	0.01 (14)	C5—C4—C8—C9A	−18.3 (3)
C3—S1—C4—C8	178.33 (16)	S1—C4—C8—C9A	163.68 (16)
C8—C4—C5—C2	−178.70 (17)	C6—C7—C9A—C10A	179.9 (3)
S1—C4—C5—C2	−0.5 (2)	C6—C7—C9A—C8	−53.9 (3)
C8—C4—C5—C6	0.6 (3)	C4—C8—C9A—C7	42.0 (3)
S1—C4—C5—C6	178.83 (14)	C4—C8—C9A—C10A	168.8 (3)
C3—C2—C5—C4	0.8 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1i	0.88	2.22	3.087 (2)	170
N2—H2B···N1ii	0.88	2.41	3.247 (2)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1i	0.88	2.22	3.087 (2)	170
N2—H2B⋯N1ii	0.88	2.41	3.247 (2)	160

Symmetry codes: (i) ; (ii) .