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

In the title compound, C(9)H(8)N(2)OS, the benzothio-phene ring is substituted with amino, oxo and carbonitrile groups. The thio-phene ring is essentially planar (r.m.s. deviation = 0.0003 Å), while the cyclo-hexene ring is in a half-chair conformation. In the crystal, N-H⋯O hydrogen bonds generate chains of mol-ecules in a zigzag pattern along the b axis. Pairs of N-H⋯N hydrogen bonds form centrosymmetric head-to-head dimers about inversion centres, corresponding to an R(2) (2)(12) graph-set motif. In addition, rather weak N-H⋯S inter-actions are also present in the structure and the supra-molecular assembly is further consolidated by π-π stacking inter-actions between the benzothio-phene rings, disposed at a distance of 3.742 (3) Å.

Related literature

For the preparation of the title compound, see: Shetty et al. (2009 ▶). For general background, see: Jordan (2003 ▶); Russell & Press (1996 ▶); Mery et al. (2002 ▶). For related structures, see: Akkurt et al. (2008 ▶); Harrison et al. (2006 ▶); Vasu et al. (2004 ▶). For Cremer–Pople puckering parameters, see: Cremer & Pople (1975 ▶). For hydrogen-bond graph-set nomenclature, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C9H8N2OS

M = 192.24

Monoclinic,

a = 7.2986 (3) Å

b = 8.7555 (3) Å

c = 14.7307 (6) Å

β = 94.151 (1)°

V = 938.87 (6) Å3

Z = 4

Mo Kα radiation

μ = 0.30 mm−1

T = 296 K

0.20 × 0.18 × 0.18 mm

Data collection

Bruker SMART APEX CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 1998 ▶) T min = 0.942, T max = 0.947

6202 measured reflections

2058 independent reflections

1671 reflections with I > 2σ(I)

R int = 0.020

Refinement

R[F 2 > 2σ(F 2)] = 0.043

wR(F 2) = 0.126

S = 1.02

2058 reflections

118 parameters

H-atom parameters constrained

Δρmax = 0.70 e Å−3

Δρmin = −0.34 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SMART; data reduction: SAINT-Plus (Bruker, 1998 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶) and PARST (Nardelli, 1983 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and CAMERON (Watkin et al., 1996 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Crystal structure: contains datablocks global, I. DOI: 10.1107/S160053681003730X/pv2326sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S160053681003730X/pv2326Isup2.hkl

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

C9H8N2OS	F(000) = 400
Mr = 192.24	Dx = 1.360 Mg m−3
Monoclinic, P21/n	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2yn	Cell parameters from 2058 reflections
a = 7.2986 (3) Å	θ = 2.7–27.0°
b = 8.7555 (3) Å	µ = 0.30 mm−1
c = 14.7307 (6) Å	T = 296 K
β = 94.151 (1)°	Block, yellow
V = 938.87 (6) Å3	0.20 × 0.18 × 0.18 mm
Z = 4

Bruker SMART APEX CCD diffractometer	2058 independent reflections
Radiation source: Enhance (Mo) X-ray Source	1671 reflections with I > 2σ(I)
graphite	Rint = 0.020
ω scans	θmax = 27.0°, θmin = 2.7°
Absorption correction: multi-scan (SADABS; Bruker, 1998)	h = −9→5
Tmin = 0.942, Tmax = 0.947	k = −11→10
6202 measured reflections	l = −18→18

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)] = 0.043	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.126	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0675P)2 + 0.447P] where P = (Fo2 + 2Fc2)/3
2058 reflections	(Δ/σ)max < 0.001
118 parameters	Δρmax = 0.70 e Å−3
0 restraints	Δρmin = −0.34 e Å−3

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

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
C1	−0.0414 (3)	1.0457 (2)	0.33340 (13)	0.0378 (4)
C2	0.1087 (3)	0.7962 (2)	0.37011 (13)	0.0386 (4)
C3	−0.0580 (3)	0.8166 (2)	0.41027 (13)	0.0391 (4)
C4	−0.3211 (3)	1.0145 (3)	0.42024 (14)	0.0430 (5)
H4A	−0.3036	1.0483	0.4830	0.052*
H4B	−0.4087	0.9310	0.4176	0.052*
C5	−0.3979 (3)	1.1460 (3)	0.3610 (2)	0.0664 (7)
H5A	−0.4533	1.1044	0.3045	0.080*
H5B	−0.4942	1.1960	0.3921	0.080*
C6	−0.2579 (3)	1.2634 (3)	0.33910 (19)	0.0588 (6)
H6A	−0.2179	1.3181	0.3943	0.071*
H6B	−0.3147	1.3366	0.2964	0.071*
C7	−0.0921 (3)	1.1943 (2)	0.29875 (14)	0.0444 (5)
C8	−0.1417 (3)	0.9590 (2)	0.38916 (13)	0.0371 (4)
C9	−0.1327 (3)	0.7027 (3)	0.46592 (16)	0.0494 (5)
N1	0.2242 (3)	0.6773 (2)	0.37766 (13)	0.0539 (5)
H1A	0.1994	0.6002	0.4108	0.065*
H1B	0.3233	0.6781	0.3494	0.065*
N2	−0.1907 (3)	0.6114 (3)	0.51076 (18)	0.0781 (7)
O1	−0.0078 (2)	1.2613 (2)	0.24138 (12)	0.0622 (5)
S1	0.15957 (6)	0.95344 (6)	0.30522 (3)	0.04133 (19)

	U11	U22	U33	U12	U13	U23
C1	0.0312 (9)	0.0402 (10)	0.0431 (10)	−0.0005 (8)	0.0107 (8)	0.0018 (8)
C2	0.0401 (10)	0.0374 (10)	0.0395 (10)	−0.0024 (8)	0.0107 (8)	0.0004 (8)
C3	0.0396 (10)	0.0402 (10)	0.0391 (10)	−0.0035 (8)	0.0126 (8)	0.0025 (8)
C4	0.0363 (10)	0.0507 (12)	0.0437 (10)	−0.0021 (9)	0.0147 (8)	−0.0008 (9)
C5	0.0440 (12)	0.0647 (16)	0.0931 (19)	0.0074 (12)	0.0246 (12)	0.0112 (14)
C6	0.0500 (13)	0.0545 (13)	0.0741 (16)	0.0128 (11)	0.0200 (12)	0.0146 (12)
C7	0.0387 (10)	0.0458 (12)	0.0499 (11)	0.0007 (9)	0.0107 (9)	0.0069 (9)
C8	0.0340 (9)	0.0421 (11)	0.0359 (9)	−0.0037 (8)	0.0080 (7)	−0.0024 (8)
C9	0.0490 (12)	0.0433 (12)	0.0585 (13)	0.0020 (9)	0.0211 (10)	0.0079 (10)
N1	0.0563 (11)	0.0431 (10)	0.0659 (12)	0.0097 (8)	0.0285 (9)	0.0104 (9)
N2	0.0778 (16)	0.0632 (14)	0.0985 (18)	0.0055 (13)	0.0416 (14)	0.0298 (14)
O1	0.0572 (10)	0.0555 (10)	0.0773 (11)	0.0072 (8)	0.0295 (8)	0.0249 (8)
S1	0.0344 (3)	0.0419 (3)	0.0496 (3)	−0.0004 (2)	0.0160 (2)	0.0072 (2)

C1—C8	1.368 (3)	C4—H4B	0.9700
C1—C7	1.437 (3)	C5—C6	1.501 (3)
C1—S1	1.7504 (19)	C5—H5A	0.9700
C2—N1	1.339 (3)	C5—H5B	0.9700
C2—C3	1.402 (3)	C6—C7	1.512 (3)
C2—S1	1.732 (2)	C6—H6A	0.9700
C3—C8	1.414 (3)	C6—H6B	0.9700
C3—C9	1.424 (3)	C7—O1	1.230 (2)
C4—C8	1.499 (3)	C9—N2	1.138 (3)
C4—C5	1.526 (3)	N1—H1A	0.8600
C4—H4A	0.9700	N1—H1B	0.8600
C8—C1—C7	125.45 (18)	C4—C5—H5B	108.7
C8—C1—S1	112.37 (15)	H5A—C5—H5B	107.6
C7—C1—S1	122.18 (15)	C5—C6—C7	112.8 (2)
N1—C2—C3	128.63 (18)	C5—C6—H6A	109.0
N1—C2—S1	120.34 (15)	C7—C6—H6A	109.0
C3—C2—S1	111.02 (15)	C5—C6—H6B	109.0
C2—C3—C8	113.20 (17)	C7—C6—H6B	109.0
C2—C3—C9	122.26 (19)	H6A—C6—H6B	107.8
C8—C3—C9	124.54 (18)	O1—C7—C1	123.17 (19)
C8—C4—C5	111.26 (17)	O1—C7—C6	122.3 (2)
C8—C4—H4A	109.4	C1—C7—C6	114.57 (18)
C5—C4—H4A	109.4	C1—C8—C3	112.31 (17)
C8—C4—H4B	109.4	C1—C8—C4	121.39 (19)
C5—C4—H4B	109.4	C3—C8—C4	126.28 (17)
H4A—C4—H4B	108.0	N2—C9—C3	179.3 (3)
C6—C5—C4	114.3 (2)	C2—N1—H1A	120.0
C6—C5—H5A	108.7	C2—N1—H1B	120.0
C4—C5—H5A	108.7	H1A—N1—H1B	120.0
C6—C5—H5B	108.7	C2—S1—C1	91.10 (9)
N1—C2—C3—C8	178.3 (2)	C7—C1—C8—C4	0.0 (3)
S1—C2—C3—C8	−0.7 (2)	S1—C1—C8—C4	−178.70 (14)
N1—C2—C3—C9	−2.1 (4)	C2—C3—C8—C1	0.4 (3)
S1—C2—C3—C9	178.95 (17)	C9—C3—C8—C1	−179.2 (2)
C8—C4—C5—C6	−43.4 (3)	C2—C3—C8—C4	179.08 (18)
C4—C5—C6—C7	52.8 (3)	C9—C3—C8—C4	−0.5 (3)
C8—C1—C7—O1	−172.2 (2)	C5—C4—C8—C1	17.3 (3)
S1—C1—C7—O1	6.4 (3)	C5—C4—C8—C3	−161.3 (2)
C8—C1—C7—C6	8.3 (3)	C2—C3—C9—N2	38 (24)
S1—C1—C7—C6	−173.14 (17)	C8—C3—C9—N2	−142 (24)
C5—C6—C7—O1	146.5 (2)	N1—C2—S1—C1	−178.50 (18)
C5—C6—C7—C1	−33.9 (3)	C3—C2—S1—C1	0.57 (16)
C7—C1—C8—C3	178.76 (19)	C8—C1—S1—C2	−0.37 (17)
S1—C1—C8—C3	0.1 (2)	C7—C1—S1—C2	−179.11 (18)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1A···N2i	0.86	2.19	3.038 (3)	169
N1—H1B···O1ii	0.86	2.10	2.903 (3)	156
N1—H1B···S1ii	0.86	3.02	3.482 (2)	116

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1A⋯N2i	0.86	2.19	3.038 (3)	169
N1—H1B⋯O1ii	0.86	2.10	2.903 (3)	156
N1—H1B⋯S1ii	0.86	3.02	3.482 (2)	116

Symmetry codes: (i) ; (ii) .