2-(2-Nitro-anilino)-4,5,6,7-tetra-hydro-benzo[b]thio-phene-3-carbonitrile.

The title compound, C(15)H(13)N(3)O(2)S, was synthesized by the reaction of 2-amino-5,6,7,8-tetra-hydro-4H-cyclo-hepta-[b]thio-phene-3-carbonitrile and o-fluoro-nitro-benzene. The dihedral angle between the thio-phene and nitro-phenyl rings is 75.15 (2)°. In the crystal, inter-molecular N-H⋯N and C-H⋯O inter-actions lead to the formation of a supra-molecular chain extending along the c-axis direction.

Related literature

For background to 2-substituted thio­phenes, see: Puterová et al. (2009 ▶). For the biological activity of 2-amino-benzo[b]thio­phene derivatives, see: Fakhr et al. (2008 ▶); Baraldi et al. (2006 ▶). For the synthesis of 2-amino thio­phenes, see: Gewald et al. (1966 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C15H13N3O2S

M = 299.34

Monoclinic,

a = 13.2764 (4) Å

b = 13.4447 (7) Å

c = 8.2237 (4) Å

β = 106.794 (2)°

V = 1405.30 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.24 mm−1

T = 295 K

0.27 × 0.19 × 0.17 mm

Data collection

Nonius KappaCCD diffractometer

9590 measured reflections

3241 independent reflections

2351 reflections with I > 2σ(I)

R int = 0.051

Refinement

R[F 2 > 2σ(F 2)] = 0.057

wR(F 2) = 0.174

S = 1.06

3241 reflections

192 parameters

H-atom parameters constrained

Δρmax = 0.45 e Å−3

Δρmin = −0.38 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 datablocks I, global. DOI: 10.1107/S1600536810035439/tk2704sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810035439/tk2704Isup2.hkl

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

C15H13N3O2S	F(000) = 624
Mr = 299.34	Dx = 1.415 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 4953 reflections
a = 13.2764 (4) Å	θ = 2.9–27.5°
b = 13.4447 (7) Å	µ = 0.24 mm−1
c = 8.2237 (4) Å	T = 295 K
β = 106.794 (2)°	Prism, yellow
V = 1405.30 (11) Å3	0.27 × 0.19 × 0.17 mm
Z = 4

Nonius KappaCCD diffractometer	2351 reflections with I > 2σ(I)
Radiation source: Enraf Nonius FR590	Rint = 0.051
horizonally mounted graphite crystal	θmax = 27.5°, θmin = 3.0°
Detector resolution: 9 pixels mm-1	h = −17→17
CCD rotation images,thick slices scans	k = −17→17
9590 measured reflections	l = −9→10
3241 independent reflections

Refinement on F2	Secondary atom site location: difference Fourier map
Least-squares matrix: full	Hydrogen site location: inferred from neighbouring sites
R[F2 > 2σ(F2)] = 0.057	H-atom parameters constrained
wR(F2) = 0.174	w = 1/[σ2(Fo2) + (0.1015P)2 + 0.2662P] where P = (Fo2 + 2Fc2)/3
S = 1.06	(Δ/σ)max < 0.001
3241 reflections	Δρmax = 0.45 e Å−3
192 parameters	Δρmin = −0.38 e Å−3
0 restraints	Extinction correction: SHELXL97 (Sheldrick, 2008), Fc*=kFc[1+0.001xFc2λ3/sin(2θ)]-1/4
Primary atom site location: structure-invariant direct methods	Extinction coefficient: 0.133 (13)

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	−0.22931 (15)	−0.11377 (16)	−0.8690 (3)	0.0489 (5)
C2	−0.17013 (15)	−0.19140 (16)	−0.7859 (2)	0.0470 (5)
C3	−0.06070 (15)	−0.16847 (17)	−0.7171 (3)	0.0494 (5)
C4	0.02377 (17)	−0.2391 (2)	−0.6205 (3)	0.0620 (6)
H4A	0.0009	−0.2717	−0.5322	0.074*
H4B	0.0352	−0.2898	−0.6972	0.074*
C5	0.1254 (2)	−0.1846 (3)	−0.5417 (5)	0.1058 (12)
H5A	0.1231	−0.1586	−0.4328	0.127*
H5B	0.1823	−0.2325	−0.5196	0.127*
C6	0.1505 (2)	−0.1041 (3)	−0.6378 (6)	0.1056 (13)
H6A	0.1667	−0.1319	−0.7362	0.127*
H6B	0.2138	−0.0720	−0.5686	0.127*
C7	0.06661 (19)	−0.0251 (2)	−0.6990 (4)	0.0700 (7)
H7A	0.0705	0.0225	−0.6088	0.084*
H7B	0.0783	0.0102	−0.7948	0.084*
C8	−0.04015 (15)	−0.07297 (18)	−0.7510 (3)	0.0540 (5)
C9	−0.41366 (15)	−0.11662 (14)	−0.8689 (3)	0.0449 (5)
C10	−0.38494 (18)	−0.10942 (18)	−0.6915 (3)	0.0560 (6)
H10	−0.3142	−0.1031	−0.6314	0.067*
C11	−0.4588 (2)	−0.1114 (2)	−0.6043 (3)	0.0649 (6)
H11	−0.4374	−0.1062	−0.4865	0.078*
C12	−0.5649 (2)	−0.1210 (2)	−0.6897 (4)	0.0703 (7)
H12	−0.6145	−0.1229	−0.6298	0.084*
C13	−0.59545 (18)	−0.12779 (18)	−0.8620 (4)	0.0622 (6)
H13	−0.6665	−0.1338	−0.9202	0.075*
C14	−0.52138 (16)	−0.12570 (15)	−0.9526 (3)	0.0486 (5)
C15	−0.21465 (15)	−0.28666 (18)	−0.7727 (3)	0.0519 (5)
N1	−0.25004 (17)	−0.36281 (16)	−0.7606 (3)	0.0673 (6)
N2	−0.33714 (13)	−0.11309 (15)	−0.9523 (2)	0.0524 (5)
H2	−0.3569	−0.1103	−1.0614	0.063*
N3	−0.56173 (15)	−0.13233 (14)	−1.1361 (3)	0.0572 (5)
O1	−0.49971 (14)	−0.12880 (15)	−1.2218 (2)	0.0713 (5)
O2	−0.65641 (14)	−0.14080 (17)	−1.2012 (3)	0.0866 (6)
S1	−0.15219 (4)	−0.01029 (5)	−0.86321 (8)	0.0610 (3)

	U11	U22	U33	U12	U13	U23
C1	0.0350 (10)	0.0626 (12)	0.0490 (11)	0.0004 (8)	0.0119 (8)	0.0021 (9)
C2	0.0348 (9)	0.0602 (12)	0.0452 (10)	0.0001 (8)	0.0105 (8)	0.0005 (9)
C3	0.0342 (10)	0.0649 (12)	0.0479 (10)	0.0015 (8)	0.0103 (8)	−0.0039 (9)
C4	0.0414 (11)	0.0756 (15)	0.0637 (13)	0.0065 (10)	0.0066 (10)	0.0019 (12)
C5	0.0452 (15)	0.113 (3)	0.134 (3)	0.0006 (15)	−0.0129 (17)	0.017 (2)
C6	0.0401 (14)	0.111 (3)	0.155 (4)	−0.0094 (14)	0.0110 (17)	0.012 (2)
C7	0.0415 (11)	0.0811 (17)	0.0843 (17)	−0.0116 (11)	0.0133 (11)	−0.0086 (14)
C8	0.0371 (10)	0.0652 (13)	0.0598 (12)	−0.0011 (9)	0.0140 (9)	−0.0044 (10)
C9	0.0365 (9)	0.0465 (10)	0.0504 (10)	0.0035 (7)	0.0104 (8)	0.0042 (8)
C10	0.0433 (11)	0.0699 (14)	0.0537 (12)	0.0050 (10)	0.0123 (9)	0.0017 (10)
C11	0.0588 (14)	0.0817 (17)	0.0590 (13)	0.0141 (12)	0.0246 (11)	0.0063 (12)
C12	0.0552 (14)	0.0834 (18)	0.0825 (18)	0.0101 (12)	0.0363 (13)	0.0121 (14)
C13	0.0391 (11)	0.0643 (14)	0.0836 (17)	0.0018 (9)	0.0182 (11)	0.0075 (12)
C14	0.0375 (10)	0.0461 (10)	0.0590 (12)	0.0030 (8)	0.0088 (9)	0.0038 (9)
C15	0.0373 (10)	0.0654 (13)	0.0502 (11)	0.0030 (9)	0.0081 (8)	0.0052 (10)
N1	0.0534 (11)	0.0684 (13)	0.0759 (13)	−0.0033 (10)	0.0121 (10)	0.0102 (10)
N2	0.0335 (8)	0.0765 (12)	0.0444 (9)	0.0030 (8)	0.0069 (7)	0.0035 (8)
N3	0.0420 (9)	0.0574 (11)	0.0631 (11)	0.0020 (8)	0.0010 (8)	−0.0018 (9)
O1	0.0580 (10)	0.0953 (14)	0.0540 (9)	−0.0013 (9)	0.0056 (8)	0.0017 (9)
O2	0.0413 (9)	0.1135 (16)	0.0871 (13)	0.0028 (9)	−0.0099 (9)	−0.0141 (11)
S1	0.0445 (4)	0.0594 (4)	0.0757 (5)	−0.0014 (2)	0.0119 (3)	0.0052 (3)

C1—C2	1.365 (3)	C7—H7B	0.9700
C1—N2	1.397 (2)	C8—S1	1.727 (2)
C1—S1	1.720 (2)	C9—N2	1.381 (2)
C2—C15	1.428 (3)	C9—C10	1.401 (3)
C2—C3	1.432 (3)	C9—C14	1.402 (3)
C3—C8	1.358 (3)	C10—C11	1.372 (3)
C3—C4	1.508 (3)	C10—H10	0.9300
C4—C5	1.507 (4)	C11—C12	1.386 (4)
C4—H4A	0.9700	C11—H11	0.9300
C4—H4B	0.9700	C12—C13	1.360 (4)
C5—C6	1.436 (5)	C12—H12	0.9300
C5—H5A	0.9700	C13—C14	1.395 (3)
C5—H5B	0.9700	C13—H13	0.9300
C6—C7	1.516 (4)	C14—N3	1.451 (3)
C6—H6A	0.9700	C15—N1	1.143 (3)
C6—H6B	0.9700	N2—H2	0.8600
C7—C8	1.502 (3)	N3—O2	1.221 (3)
C7—H7A	0.9700	N3—O1	1.230 (3)
C2—C1—N2	127.62 (19)	C6—C7—H7B	109.7
C2—C1—S1	110.65 (15)	H7A—C7—H7B	108.2
N2—C1—S1	121.72 (16)	C3—C8—C7	125.1 (2)
C1—C2—C15	122.20 (18)	C3—C8—S1	112.21 (15)
C1—C2—C3	113.87 (19)	C7—C8—S1	122.6 (2)
C15—C2—C3	123.92 (19)	N2—C9—C10	119.80 (18)
C8—C3—C2	111.30 (19)	N2—C9—C14	123.48 (19)
C8—C3—C4	122.69 (19)	C10—C9—C14	116.71 (19)
C2—C3—C4	126.0 (2)	C11—C10—C9	121.5 (2)
C5—C4—C3	111.0 (2)	C11—C10—H10	119.2
C5—C4—H4A	109.4	C9—C10—H10	119.2
C3—C4—H4A	109.4	C10—C11—C12	120.8 (2)
C5—C4—H4B	109.4	C10—C11—H11	119.6
C3—C4—H4B	109.4	C12—C11—H11	119.6
H4A—C4—H4B	108.0	C13—C12—C11	119.2 (2)
C6—C5—C4	116.8 (3)	C13—C12—H12	120.4
C6—C5—H5A	108.1	C11—C12—H12	120.4
C4—C5—H5A	108.1	C12—C13—C14	120.7 (2)
C6—C5—H5B	108.1	C12—C13—H13	119.6
C4—C5—H5B	108.1	C14—C13—H13	119.6
H5A—C5—H5B	107.3	C13—C14—C9	121.1 (2)
C5—C6—C7	116.4 (3)	C13—C14—N3	116.7 (2)
C5—C6—H6A	108.2	C9—C14—N3	122.25 (19)
C7—C6—H6A	108.2	N1—C15—C2	179.4 (2)
C5—C6—H6B	108.2	C9—N2—C1	123.57 (17)
C7—C6—H6B	108.2	C9—N2—H2	118.2
H6A—C6—H6B	107.3	C1—N2—H2	118.2
C8—C7—C6	109.7 (2)	O2—N3—O1	121.8 (2)
C8—C7—H7A	109.7	O2—N3—C14	119.0 (2)
C6—C7—H7A	109.7	O1—N3—C14	119.12 (18)
C8—C7—H7B	109.7	C1—S1—C8	91.95 (10)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···N1i	0.86	2.48	3.093 (3)	129
C11—H11···O1ii	0.93	2.56	3.351 (3)	143

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯N1i	0.86	2.48	3.093 (3)	129
C11—H11⋯O1ii	0.93	2.56	3.351 (3)	143

Symmetry codes: (i) ; (ii) .