2-Amino-7-oxo-4,5,6,7-tetra­hydro-1-benzothio­phene-3-carbonitrile

Ziaulla, M.; Banu, A.; Begum, N.S.; Panchamukhi, S.I.; Khazi, I.M.

doi:10.1107/S160053681003730X

organic compounds

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ISSN: 2056-9890

Volume 66| Part 10| October 2010| Pages o2616-o2617

doi:10.1107/S160053681003730X

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2-Amino-7-oxo-4,5,6,7-tetrahydro-1-benzothiophene-3-carbonitrile

Mohamed Ziaulla,^a Afshan Banu,^a Noor Shahina Begum,^a ^* Shridhar I. Panchamukhi ^b and I. M. Khazi ^b

^aDepartment of Studies in Chemistry, Bangalore University, Bangalore 560 001, Karnataka, India, and ^bDepartment of Chemistry, Karnatak University, Dharwad 580 003, India
^*Correspondence e-mail: noorsb@rediffmail.com

(Received 27 August 2010; accepted 17 September 2010; online 25 September 2010)

In the title compound, C₉H₈N₂OS, the benzothiophene ring is substituted with amino, oxo and carbonitrile groups. The thiophene ring is essentially planar (r.m.s. deviation = 0.0003 Å), while the cyclohexene ring is in a half-chair conformation. In the crystal, N—H⋯O hydrogen bonds generate chains of molecules 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 R₂²(12) graph-set motif. In addition, rather weak N—H⋯S interactions are also present in the structure and the supramolecular assembly is further consolidated by π–π stacking interactions between the benzothiophene 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_r = 192.24
Monoclinic, P 2₁ /n
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[F² > 2σ(F²)] = 0.043
wR(F²) = 0.126
S = 1.02
2058 reflections
118 parameters
H-atom parameters constrained
Δρ_max = 0.70 e Å⁻³
Δρ_min = −0.34 e Å⁻³

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) -x, -y+1, -z+1; (ii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ .

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 ).

Supporting information

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

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

checkCIF report

Comment top

Benzothiophenes are important biologically active molecules. One of the most important drugs based on the benzothiophene system is Raloxifene, used for the prevention and treatment of osteoporosis in postmenopausal women (Jordan, 2003). Benzothiophenes are also luminescent components used in organic materials (Russell & Press, 1996). In addition, they are regarded as important units in liquid crystal research (Mery et al., 2002). In this article, we report the structure of the title compound which has been synthesized in our laboratory.

In the title compound (Fig. 1), the thiophene ring is essentially planar while the cyclohexene ring is in a half-chair conformation; the atoms C5 and C6 deviate from the mean plane C1/C7/C4/C8 by 0.341 (3)and -0.233 (2) Å, respectively. The puckering parameters (Cremer & Pople, 1975) for the cyclohexene ring are: Q(2) = 0.3175 (3) Å, ϕ(2) = -17.96 (8)° and θ = 129.68 (7)°. In several benzothiophene derivatives the cyclohexyl ring adopts half-chair conformation, e.g., (Akkurt et al., 2008; Harrison et al., 2006; Vasu et al., 2004).

The N—H···O hydrogen bonds generate chains of molecules in a zigzag pattern along the b-axis. While the N—H···N hydrogen bonds form centrosymmetric, head-to-head dimers about inversion centers corresponding to graph set R²₂(12) motif. In addition, rather weak N—H···S interactions are also present in the structure and the supramolecular assembly is further consolidated by π–π-stacking interactions between the benzothiophene rings; C—C disposed at a distance of 3.742 (3) Å.

The intermolecular interactions of the type N—H···O, N—H···N and N—H···S stabilize the crystal structure (Table 1). The N1—H1A···O1 hydrogen bonds generate chains of molecules in a zigzag pattern along the b-axis (Fig. 2). The N1—H1B···N2 hydrogen bonds on the other hand, form centrosymmetric, head-to-head dimers about inversion centers corresponding to graph set R²₂(12) motif (Bernstein et al., 1995) (Fig. 2). In addition, rather weak N1—H1B···S1 interactions are also present in the structure and the supramolecular assembly is further consolidated by π–π-stacking interactions between the benzothiophene rings; C—C disposed at a distance of 3.742 (3) Å.

Related literature top

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 top

The title compound was synthesized by following the procedure reported earlier (Shetty et al., 2009).

Computing details top

Data collection: SMART (Bruker, 1998); cell refinement: SMART (Bruker, 1998); data reduction: SAINT-Plus (Bruker, 1998); 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 CAMERON (Watkin et al., 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. ORTEP (Farrugia, 1997) view of the title compound, showing 50% probability ellipsoids and the atom numbering scheme.
	Fig. 2. A unit cell packing of the title compound showing intermolecular hydrogen bonds with dotted lines. H atoms not involved in hydrogen bonding have been excluded.

2-Amino-7-oxo-4,5,6,7-tetrahydro-1-benzothiophene-3-carbonitrile top

Crystal data top

C₉H₈N₂OS	F(000) = 400
M_r = 192.24	D_x = 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

Data collection top

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

Refinement top

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(F_o²) + (0.0675P)² + 0.447P] where P = (F_o² + 2F_c²)/3
2058 reflections	(Δ/σ)_max < 0.001
118 parameters	Δρ_max = 0.70 e Å⁻³
0 restraints	Δρ_min = −0.34 e Å⁻³

Crystal data top

C₉H₈N₂OS	V = 938.87 (6) Å³
M_r = 192.24	Z = 4
Monoclinic, P2₁/n	Mo Kα radiation
a = 7.2986 (3) Å	µ = 0.30 mm⁻¹
b = 8.7555 (3) Å	T = 296 K
c = 14.7307 (6) Å	0.20 × 0.18 × 0.18 mm
β = 94.151 (1)°

Data collection top

Bruker SMART APEX CCD diffractometer	2058 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1671 reflections with I > 2σ(I)
T_min = 0.942, T_max = 0.947	R_int = 0.020
6202 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.043	0 restraints
wR(F²) = 0.126	H-atom parameters constrained
S = 1.02	Δρ_max = 0.70 e Å⁻³
2058 reflections	Δρ_min = −0.34 e Å⁻³
118 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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) −x, −y+1, −z+1; (ii) −x+1/2, y−1/2, −z+1/2.

Experimental details

Crystal data
Chemical formula	C₉H₈N₂OS
M_r	192.24
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.2986 (3), 8.7555 (3), 14.7307 (6)
β (°)	94.151 (1)
V (Å³)	938.87 (6)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.30
Crystal size (mm)	0.20 × 0.18 × 0.18

Data collection
Diffractometer	Bruker SMART APEX CCD diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.942, 0.947
No. of measured, independent and observed [I > 2σ(I)] reflections	6202, 2058, 1671
R_int	0.020
(sin θ/λ)_max (Å⁻¹)	0.639

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.126, 1.02
No. of reflections	2058
No. of parameters	118
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.70, −0.34

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), ORTEP-3 (Farrugia, 1997) and CAMERON (Watkin et al., 1996), WinGX (Farrugia, 1999).

Hydrogen-bond geometry (Å, º) top

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) −x, −y+1, −z+1; (ii) −x+1/2, y−1/2, −z+1/2.

Acknowledgements

NSB is grateful to the University Grants Commission (UGC), India, for financial assistance, and the Department of Science and Technology (DST), India, for the data-collection facility under the IRHPA–DST programme.

References

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