2-Amino-6-methyl-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/S1600536811006076

organic compounds

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ISSN: 2056-9890

Volume 67| Part 3| March 2011| Page o699

doi:10.1107/S1600536811006076

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2-Amino-6-methyl-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, India, and ^bDepartment of Chemistry, Karnatak University, Dharwad 580 003, India
^*Correspondence e-mail: noorsb@rediffmail.com

(Received 25 January 2011; accepted 17 February 2011; online 23 February 2011)

In the title compound, C₁₀H₁₂N₂S, one of the C atoms of the cyclohexene 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 cyclohexene ring in both the major and minor occupancy conformers adopts a half-chair conformation. The thiophene 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 R₂²(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_r = 192.29
Monoclinic, P 2₁ /c
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[F² > 2σ(F²)] = 0.040
wR(F²) = 0.107
S = 1.07
2441 reflections
127 parameters
H-atom parameters constrained
Δρ_max = 0.39 e Å⁻³
Δρ_min = −0.30 e Å⁻³

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

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 ).

Supporting information

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

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

checkCIF report

Comment top

Benzothiophenes are important heterocycles either as biological active molecules or as luminescent components used in organic materials (Shishoo & Jain, 1992; Katritzky et al., 1996). In this paper, we report the crystal structure of a benzothiophene derivative.

In the title compound (Fig. 1), the fused benzothiophene ring system is substituted with amino, methyl and carbonitrile groups. The carbon atoms C9 and C10 are disordered over two sites (C9A/C9B and C10A/C10B) with site occupancy factors 0.650 (3) and 0.350 (3) resulting in a major and a minor conformers. The cyclohexene ring in both conformers is in a half-chair conformation with C9A and C9B 0.547 (4) and 0.506 (6) Å, respectively, displaced on the opposite sides from the plane formed by the rest of the ring C-atoms (max. deviation being 0.063 (2) Å for C6). The thiophene ring is essentially planar. In several benzothiophene derivatives the cyclohexyl ring adopts half-chair conformation (Akkurt et al., 2008; Harrison et al., 2006; Vasu et al., 2004). The crystal structure is stabilized by two types of N—H···N intermolecular interactions (Table 1); N2—H2A···N1 hydrogen bond forms centrosymmetric, head-to-head dimers about inversion centers corresponding to graph set R²₂(12) motif(Bernstein et al., 1995) while N2—H2B···N1 hydrogen bonds generate chains of molecules in a zigzag pattern along the a axis (Fig. 2).

Related literature top

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 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: SAINT-Plus (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: CAMERON (Watkin et al., 1996); software used to prepare material for publication: WinGX (Farrugia, 1999).

Figures top

	Fig. 1. ORTEP (Farrugia, 1999) view of the title compound, showing 50% probability ellipsoids and the atom numbering scheme; C-atoms C9b and C10b represent the minor conformer.
	Fig. 2. A unit cell packing of the title compound showing intermolecular interactions with dotted lines. H-atoms not involved in hydrogen bonding have been excluded.

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

Crystal data top

C₁₀H₁₂N₂S	F(000) = 408
M_r = 192.29	D_x = 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

Data collection top

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

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)] = 0.040	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.107	H-atom parameters constrained
S = 1.07	w = 1/[σ²(F_o²) + (0.0536P)² + 0.2028P] where P = (F_o² + 2F_c²)/3
2441 reflections	(Δ/σ)_max = 0.001
127 parameters	Δρ_max = 0.39 e Å⁻³
0 restraints	Δρ_min = −0.30 e Å⁻³

Crystal data top

C₁₀H₁₂N₂S	V = 988.69 (4) Å³
M_r = 192.29	Z = 4
Monoclinic, P2₁/c	Mo Kα radiation
a = 9.0415 (2) Å	µ = 0.28 mm⁻¹
b = 8.3294 (2) Å	T = 123 K
c = 13.1283 (3) Å	0.16 × 0.16 × 0.14 mm
β = 90.169 (2)°

Data collection top

Bruker SMART APEX CCD detector diffractometer	2441 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 1998)	1878 reflections with I > 2σ(I)
T_min = 0.957, T_max = 0.962	R_int = 0.039
11284 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.040	0 restraints
wR(F²) = 0.107	H-atom parameters constrained
S = 1.07	Δρ_max = 0.39 e Å⁻³
2441 reflections	Δρ_min = −0.30 e Å⁻³
127 parameters

Special details top

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.

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

	x	y	z	U_iso*/U_eq	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)

Atomic displacement parameters (Å²) top

	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)

Geometric parameters (Å, º) top

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)

Hydrogen-bond geometry (Å, º) top

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

Experimental details

Crystal data
Chemical formula	C₁₀H₁₂N₂S
M_r	192.29
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	123
a, b, c (Å)	9.0415 (2), 8.3294 (2), 13.1283 (3)
β (°)	90.169 (2)
V (Å³)	988.69 (4)
Z	4
Radiation type	Mo Kα
µ (mm⁻¹)	0.28
Crystal size (mm)	0.16 × 0.16 × 0.14

Data collection
Diffractometer	Bruker SMART APEX CCD detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 1998)
T_min, T_max	0.957, 0.962
No. of measured, independent and observed [I > 2σ(I)] reflections	11284, 2441, 1878
R_int	0.039
(sin θ/λ)_max (Å⁻¹)	0.687

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.040, 0.107, 1.07
No. of reflections	2441
No. of parameters	127
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.39, −0.30

Computer programs: SMART (Bruker, 1998), SAINT-Plus (Bruker, 1998), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), 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
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) −x+1, −y−1, −z+1; (ii) x, −y−1/2, z−1/2.

Acknowledgements

NSB is thankful 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 program.

References

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