2-Amino-4,5,6,7-tetra-hydro-benzo[b]thio-phene-3-carbonitrile.

The title compound, C(9)H(10)N(2)S, was synthesized according to Gewald procedures by the reaction of cyclo-hexa-none with malonitrile and sulfur in the presence morpholine. The cyclo-hexane ring adopts a half-chair conformation and the thio-phene ring is essentially planar (r.m.s. deviation = 0.05 Å). The crystal packing is stabilized by two inter-molecular N-H⋯N hydrogen bonds, which link the mol-ecules into centrosymmetric rings with graph-set motif R(2) (2)(12).

Related literature

For background to 2-amino thio­phenes, see: Puterová et al. (2009 ▶). For anti­arrhythmic and serotonin antagonist properties of 2-substituted thio­phene derivatives, see: Amr et al. (2010 ▶). For their analgesic or anti-inflammatory activity, see: Hafez & El-Gazzar (2008 ▶). For the synthesis of 2-amino thio­phenes, see: Gewald et al. (1966 ▶); Wang et al. (2010 ▶). For similar structures, see: Larson & Simonsen (1988 ▶); Mendonça Junior et al. (2010 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C9H10N2S

M = 178.25

Monoclinic,

a = 10.4274 (3) Å

b = 8.1487 (3) Å

c = 13.2342 (4) Å

β = 126.937 (2)°

V = 898.81 (5) Å3

Z = 4

Mo Kα radiation

μ = 0.30 mm−1

T = 295 K

0.22 × 0.22 × 0.20 mm

Data collection

Nonius KappaCCD diffractometer

12462 measured reflections

2058 independent reflections

1630 reflections with I > 2σ(I)

R int = 0.052

Refinement

R[F 2 > 2σ(F 2)] = 0.045

wR(F 2) = 0.137

S = 1.04

2058 reflections

109 parameters

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.36 e Å−3

Data collection: COLLECT (Nonius, 1997 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811045338/bx2379sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811045338/bx2379Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811045338/bx2379Isup3.cml

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

C9H10N2S	F(000) = 376
Mr = 178.25	Dx = 1.317 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6505 reflections
a = 10.4274 (3) Å	θ = 2.6–27.5°
b = 8.1487 (3) Å	µ = 0.30 mm−1
c = 13.2342 (4) Å	T = 295 K
β = 126.937 (2)°	Prism, yellow
V = 898.81 (5) Å3	0.22 × 0.22 × 0.20 mm
Z = 4

Nonius KappaCCD diffractometer	1630 reflections with I > 2σ(I)
Radiation source: Enraf–Nonius FR590	Rint = 0.052
horizonally mounted graphite crystal	θmax = 27.5°, θmin = 3.1°
Detector resolution: 9 pixels mm-1	h = −13→13
CCD rotation images,thick slices scans	k = −10→10
12462 measured reflections	l = −17→17
2058 independent 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) = 0.137	H-atom parameters constrained
S = 1.04	w = 1/[σ2(Fo2) + (0.1P)2] where P = (Fo2 + 2Fc2)/3
2058 reflections	(Δ/σ)max = 0.001
109 parameters	Δρmax = 0.19 e Å−3
0 restraints	Δρmin = −0.36 e Å−3

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'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 > σ(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
S1	0.22127 (5)	0.01327 (5)	0.27769 (4)	0.0543 (2)
N1	0.0577 (2)	−0.37778 (18)	−0.07760 (14)	0.0648 (4)
N2	0.07860 (18)	−0.28276 (18)	0.20995 (14)	0.0603 (4)
H2A	0.0428	−0.3698	0.1640	0.072*
H2B	0.0719	−0.2727	0.2713	0.072*
C1	0.16686 (17)	−0.15535 (17)	0.09245 (13)	0.0426 (3)
C2	0.24712 (19)	−0.00893 (18)	0.09686 (15)	0.0445 (4)
C3	0.2917 (2)	0.0288 (2)	0.01054 (17)	0.0532 (4)
H3A	0.1965	0.0603	−0.0720	0.064*
H3B	0.3365	−0.0684	0.0002	0.064*
C4	0.4146 (2)	0.1681 (2)	0.06489 (19)	0.0662 (5)
H4A	0.5188	0.1265	0.1345	0.079*
H4B	0.4235	0.2079	0.0003	0.079*
C5	0.3678 (2)	0.3083 (2)	0.1112 (2)	0.0690 (5)
H5A	0.2627	0.3485	0.0419	0.083*
H5B	0.4439	0.3974	0.1389	0.083*
C6	0.3640 (2)	0.2565 (2)	0.22012 (18)	0.0641 (5)
H6A	0.4725	0.2486	0.2975	0.077*
H6B	0.3068	0.3380	0.2325	0.077*
C7	0.28162 (17)	0.0932 (2)	0.19015 (15)	0.0499 (4)
C8	0.14543 (17)	−0.16192 (19)	0.18582 (13)	0.0451 (4)
C9	0.10751 (18)	−0.27940 (19)	−0.00076 (14)	0.0477 (4)

	U11	U22	U33	U12	U13	U23
S1	0.0624 (3)	0.0552 (3)	0.0567 (3)	−0.01030 (17)	0.0419 (3)	−0.01544 (17)
N1	0.0984 (12)	0.0474 (8)	0.0663 (9)	−0.0081 (8)	0.0589 (9)	−0.0091 (7)
N2	0.0834 (10)	0.0550 (9)	0.0623 (8)	−0.0155 (7)	0.0543 (8)	−0.0106 (6)
C1	0.0474 (7)	0.0386 (7)	0.0442 (7)	0.0030 (6)	0.0288 (6)	−0.0003 (6)
C2	0.0430 (8)	0.0457 (8)	0.0457 (8)	0.0023 (6)	0.0271 (7)	0.0008 (6)
C3	0.0579 (10)	0.0550 (10)	0.0544 (9)	0.0025 (7)	0.0378 (8)	0.0051 (7)
C4	0.0629 (10)	0.0718 (13)	0.0748 (11)	−0.0065 (9)	0.0472 (9)	0.0060 (9)
C5	0.0694 (11)	0.0575 (11)	0.0780 (12)	−0.0141 (9)	0.0432 (10)	−0.0016 (9)
C6	0.0630 (10)	0.0561 (10)	0.0719 (11)	−0.0175 (8)	0.0398 (9)	−0.0164 (8)
C7	0.0469 (8)	0.0497 (9)	0.0539 (8)	−0.0047 (6)	0.0308 (7)	−0.0056 (7)
C8	0.0466 (7)	0.0441 (8)	0.0468 (8)	0.0014 (6)	0.0292 (7)	−0.0020 (6)
C9	0.0618 (9)	0.0409 (8)	0.0500 (8)	0.0028 (6)	0.0387 (7)	0.0026 (6)

S1—C8	1.7280 (15)	C3—H3A	0.9700
S1—C7	1.7432 (17)	C3—H3B	0.9700
N1—C9	1.145 (2)	C4—C5	1.509 (3)
N2—C8	1.351 (2)	C4—H4A	0.9700
N2—H2A	0.8600	C4—H4B	0.9700
N2—H2B	0.8600	C5—C6	1.526 (3)
C1—C8	1.383 (2)	C5—H5A	0.9700
C1—C9	1.417 (2)	C5—H5B	0.9700
C1—C2	1.438 (2)	C6—C7	1.502 (2)
C2—C7	1.346 (2)	C6—H6A	0.9700
C2—C3	1.502 (2)	C6—H6B	0.9700
C3—C4	1.530 (2)
C8—S1—C7	92.09 (7)	H4A—C4—H4B	108.0
C8—N2—H2A	120.0	C4—C5—C6	111.88 (16)
C8—N2—H2B	120.0	C4—C5—H5A	109.2
H2A—N2—H2B	120.0	C6—C5—H5A	109.2
C8—C1—C9	121.99 (14)	C4—C5—H5B	109.2
C8—C1—C2	113.48 (13)	C6—C5—H5B	109.2
C9—C1—C2	124.47 (13)	H5A—C5—H5B	107.9
C7—C2—C1	112.23 (14)	C7—C6—C5	109.33 (15)
C7—C2—C3	122.47 (14)	C7—C6—H6A	109.8
C1—C2—C3	125.29 (14)	C5—C6—H6A	109.8
C2—C3—C4	110.43 (14)	C7—C6—H6B	109.8
C2—C3—H3A	109.6	C5—C6—H6B	109.8
C4—C3—H3A	109.6	H6A—C6—H6B	108.3
C2—C3—H3B	109.6	C2—C7—C6	125.82 (15)
C4—C3—H3B	109.6	C2—C7—S1	111.97 (12)
H3A—C3—H3B	108.1	C6—C7—S1	122.20 (13)
C5—C4—C3	111.65 (15)	N2—C8—C1	128.53 (14)
C5—C4—H4A	109.3	N2—C8—S1	121.26 (11)
C3—C4—H4A	109.3	C1—C8—S1	110.21 (11)
C5—C4—H4B	109.3	N1—C9—C1	178.84 (18)
C3—C4—H4B	109.3

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2A···N1i	0.86	2.28	3.121 (2)	166
N2—H2B···N1ii	0.86	2.42	3.225 (3)	155

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2A⋯N1i	0.86	2.28	3.121 (2)	166
N2—H2B⋯N1ii	0.86	2.42	3.225 (3)	155

Symmetry codes: (i) ; (ii) .