2-(2-Nitro-anilino)-5,6,7,8-tetra-hydro-4H-cyclo-hepta-[b]thio-phene-3-carbonitrile.

The title compound, C(16)H(15)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 thio-phene and nitro-phenyl rings and amino and carbonitrile groups are coplanar with a maximum deviation of 0.046 (2) Å and a dihedral angle of 0.92 (6)° between the rings. The cyclo-hepta ring adopts a chair conformation. Intra-molecular N-H⋯O and C-H⋯S inter-actions occur. In the crystal, the mol-ecules form layers that are linked by π-π stacking inter-actions between the thio-phene and benzene rings [centroid-centroid distances = 3.7089 (12) and 3.6170 (12) Å].

Related literature

For background to 2-substituted thio­phenes, see: Campaigne (1984 ▶); Kleemann et al. (2006 ▶). For the biological activity of 2-amino thio­phene derivatives, see: Chakrabarti et al. (1982 ▶); Calligaro et al. (1997 ▶); Nikolakopoulos et al. (2006 ▶). For the synthesis of 2-amino thio­phenes, see: Gewald (1965 ▶); Gewald et al. (1966 ▶); Sridhar et al. (2007 ▶). For related structures, see: Stephenson et al. (1995 ▶); Yu (2002 ▶); Chen et al. (2005 ▶). For bond-length data, see: Allen et al. (1987 ▶). For puckering parameters, see: Cremer & Pople (1975 ▶).

Experimental

Crystal data

C16H15N3O2S

M = 313.37

Monoclinic,

a = 7.0273 (3) Å

b = 14.4569 (6) Å

c = 14.8867 (7) Å

β = 97.571 (2)°

V = 1499.18 (11) Å3

Z = 4

Mo Kα radiation

μ = 0.23 mm−1

T = 295 K

0.35 × 0.32 × 0.27 mm

Data collection

Nonius KappaCCD diffractometer

9360 measured reflections

3147 independent reflections

2452 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.052

wR(F 2) = 0.162

S = 1.07

3147 reflections

200 parameters

H-atom parameters constrained

Δρmax = 0.29 e Å−3

Δρmin = −0.31 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/S1600536810017149/dn2562sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810017149/dn2562Isup2.hkl

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

C16H15N3O2S	F(000) = 656
Mr = 313.37	Dx = 1.388 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 6392 reflections
a = 7.0273 (3) Å	θ = 2.9–26.7°
b = 14.4569 (6) Å	µ = 0.23 mm−1
c = 14.8867 (7) Å	T = 295 K
β = 97.571 (2)°	Prism, colorless
V = 1499.18 (11) Å3	0.35 × 0.32 × 0.27 mm
Z = 4

Nonius KappaCCD diffractometer	2452 reflections with I > 2σ(I)
Radiation source: Enraf Nonius FR590	Rint = 0.046
horizonally mounted graphite crystal	θmax = 26.6°, θmin = 3.1°
Detector resolution: 9 pixels mm-1	h = −8→8
CCD rotation images,thick slices scans	k = −15→18
9360 measured reflections	l = −18→18
3147 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)] = 0.052	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.162	H-atom parameters constrained
S = 1.07	w = 1/[σ2(Fo2) + (0.1026P)2 + 0.1476P] where P = (Fo2 + 2Fc2)/3
3147 reflections	(Δ/σ)max = 0.001
200 parameters	Δρmax = 0.29 e Å−3
0 restraints	Δρmin = −0.30 e Å−3

Geometry. All esds (except the esd in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell esds are taken into account individually in the estimation of esds in distances, angles and torsion angles; correlations between esds in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell esds is used for estimating esds 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	0.29875 (7)	0.33887 (3)	0.05524 (3)	0.0529 (2)
O1	0.1864 (3)	0.64817 (11)	−0.14472 (10)	0.0763 (5)
O2	0.1729 (3)	0.78484 (12)	−0.09126 (12)	0.0887 (6)
N1	0.2433 (2)	0.50661 (11)	−0.03762 (10)	0.0531 (4)
H1	0.2277	0.5305	−0.0910	0.064*
N2	0.1906 (2)	0.70191 (13)	−0.07994 (12)	0.0594 (4)
N3	0.2128 (4)	0.44432 (17)	−0.26828 (13)	0.0871 (7)
C1	0.2620 (2)	0.41167 (13)	−0.03697 (12)	0.0474 (4)
C2	0.2544 (3)	0.36042 (14)	−0.11578 (12)	0.0501 (4)
C3	0.2772 (3)	0.26261 (14)	−0.10156 (13)	0.0527 (5)
C4	0.2731 (4)	0.19525 (16)	−0.17935 (14)	0.0673 (6)
H4A	0.4041	0.1775	−0.1850	0.081*
H4B	0.2221	0.2269	−0.2348	0.081*
C5	0.1554 (3)	0.10721 (16)	−0.17147 (15)	0.0688 (6)
H5A	0.0271	0.1251	−0.1609	0.083*
H5B	0.1438	0.0750	−0.2291	0.083*
C6	0.2345 (4)	0.04019 (15)	−0.09784 (16)	0.0707 (6)
H6A	0.3688	0.0293	−0.1031	0.085*
H6B	0.1677	−0.0183	−0.1086	0.085*
C7	0.2190 (4)	0.07060 (16)	−0.00136 (16)	0.0710 (6)
H7A	0.0872	0.0888	0.0021	0.085*
H7B	0.2471	0.0179	0.0385	0.085*
C8	0.3487 (4)	0.14916 (15)	0.03367 (16)	0.0669 (6)
H8A	0.4798	0.1324	0.0270	0.080*
H8B	0.3418	0.1564	0.0979	0.080*
C9	0.3044 (3)	0.24118 (14)	−0.01205 (13)	0.0551 (5)
C10	0.2447 (2)	0.57016 (13)	0.03089 (12)	0.0473 (4)
C11	0.2192 (3)	0.66561 (13)	0.01206 (13)	0.0491 (4)
C12	0.2185 (3)	0.73041 (15)	0.08074 (14)	0.0587 (5)
H12	0.2012	0.7927	0.0663	0.070*
C13	0.2430 (3)	0.70360 (16)	0.16918 (15)	0.0635 (5)
H13	0.2427	0.7472	0.2151	0.076*
C14	0.2683 (3)	0.61106 (16)	0.18993 (14)	0.0636 (5)
H14	0.2845	0.5924	0.2503	0.076*
C15	0.2700 (3)	0.54584 (15)	0.12264 (13)	0.0594 (5)
H15	0.2884	0.4840	0.1386	0.071*
C16	0.2285 (3)	0.40474 (15)	−0.20159 (13)	0.0594 (5)

	U11	U22	U33	U12	U13	U23
S1	0.0672 (3)	0.0504 (3)	0.0413 (3)	−0.00605 (19)	0.0074 (2)	0.00132 (18)
O1	0.1190 (14)	0.0599 (10)	0.0478 (8)	−0.0002 (8)	0.0034 (8)	0.0025 (7)
O2	0.1394 (16)	0.0503 (10)	0.0753 (11)	0.0042 (9)	0.0103 (10)	0.0123 (8)
N1	0.0707 (10)	0.0480 (9)	0.0407 (8)	−0.0010 (7)	0.0077 (7)	0.0000 (7)
N2	0.0684 (10)	0.0538 (10)	0.0558 (10)	−0.0019 (7)	0.0072 (8)	0.0042 (8)
N3	0.1274 (18)	0.0861 (15)	0.0481 (11)	0.0209 (13)	0.0123 (10)	0.0112 (10)
C1	0.0508 (9)	0.0485 (10)	0.0427 (9)	−0.0040 (7)	0.0061 (7)	0.0005 (7)
C2	0.0563 (10)	0.0523 (10)	0.0422 (9)	−0.0028 (8)	0.0078 (7)	0.0000 (8)
C3	0.0604 (10)	0.0505 (10)	0.0475 (10)	−0.0033 (8)	0.0084 (8)	−0.0032 (8)
C4	0.0929 (15)	0.0587 (12)	0.0513 (11)	−0.0070 (11)	0.0131 (10)	−0.0077 (10)
C5	0.0836 (14)	0.0569 (12)	0.0647 (13)	0.0012 (10)	0.0048 (11)	−0.0140 (10)
C6	0.0909 (16)	0.0494 (12)	0.0705 (14)	−0.0006 (11)	0.0057 (11)	−0.0047 (10)
C7	0.0915 (15)	0.0502 (12)	0.0715 (14)	−0.0034 (10)	0.0116 (11)	0.0040 (11)
C8	0.0859 (14)	0.0559 (13)	0.0566 (12)	−0.0038 (10)	0.0010 (10)	0.0049 (9)
C9	0.0650 (11)	0.0505 (11)	0.0497 (10)	−0.0063 (8)	0.0069 (8)	−0.0009 (8)
C10	0.0481 (9)	0.0511 (10)	0.0432 (9)	−0.0042 (7)	0.0081 (7)	−0.0011 (8)
C11	0.0493 (9)	0.0508 (11)	0.0474 (10)	−0.0045 (7)	0.0071 (7)	0.0001 (7)
C12	0.0653 (11)	0.0520 (11)	0.0597 (12)	0.0000 (9)	0.0120 (9)	−0.0070 (9)
C13	0.0725 (13)	0.0632 (13)	0.0569 (11)	−0.0048 (10)	0.0169 (9)	−0.0144 (10)
C14	0.0811 (13)	0.0665 (13)	0.0448 (11)	−0.0042 (10)	0.0147 (9)	−0.0043 (9)
C15	0.0786 (13)	0.0532 (11)	0.0478 (11)	−0.0023 (10)	0.0134 (9)	0.0008 (9)
C16	0.0750 (12)	0.0587 (12)	0.0442 (10)	0.0058 (9)	0.0066 (8)	−0.0043 (9)

S1—C1	1.7220 (18)	C6—C7	1.520 (3)
S1—C9	1.735 (2)	C6—H6A	0.9700
O1—N2	1.236 (2)	C6—H6B	0.9700
O2—N2	1.215 (2)	C7—C8	1.506 (3)
N1—C10	1.372 (2)	C7—H7A	0.9700
N1—C1	1.379 (2)	C7—H7B	0.9700
N1—H1	0.8600	C8—C9	1.508 (3)
N2—C11	1.456 (2)	C8—H8A	0.9700
N3—C16	1.139 (3)	C8—H8B	0.9700
C1—C2	1.383 (2)	C10—C15	1.399 (3)
C2—C16	1.419 (3)	C10—C11	1.415 (3)
C2—C3	1.436 (3)	C11—C12	1.387 (3)
C3—C9	1.357 (3)	C12—C13	1.361 (3)
C3—C4	1.510 (3)	C12—H12	0.9300
C4—C5	1.531 (3)	C13—C14	1.379 (3)
C4—H4A	0.9700	C13—H13	0.9300
C4—H4B	0.9700	C14—C15	1.377 (3)
C5—C6	1.513 (3)	C14—H14	0.9300
C5—H5A	0.9700	C15—H15	0.9300
C5—H5B	0.9700
C1—S1—C9	92.84 (9)	C8—C7—C6	115.5 (2)
C10—N1—C1	132.09 (16)	C8—C7—H7A	108.4
C10—N1—H1	114.0	C6—C7—H7A	108.4
C1—N1—H1	114.0	C8—C7—H7B	108.4
O2—N2—O1	121.38 (19)	C6—C7—H7B	108.4
O2—N2—C11	119.03 (18)	H7A—C7—H7B	107.5
O1—N2—C11	119.59 (17)	C7—C8—C9	115.43 (19)
N1—C1—C2	122.32 (17)	C7—C8—H8A	108.4
N1—C1—S1	128.18 (14)	C9—C8—H8A	108.4
C2—C1—S1	109.50 (14)	C7—C8—H8B	108.4
C1—C2—C16	120.52 (18)	C9—C8—H8B	108.4
C1—C2—C3	114.31 (17)	H8A—C8—H8B	107.5
C16—C2—C3	125.17 (18)	C3—C9—C8	129.69 (19)
C9—C3—C2	111.61 (17)	C3—C9—S1	111.73 (15)
C9—C3—C4	126.28 (19)	C8—C9—S1	118.46 (15)
C2—C3—C4	122.11 (18)	N1—C10—C15	123.03 (18)
C3—C4—C5	115.66 (17)	N1—C10—C11	121.17 (16)
C3—C4—H4A	108.4	C15—C10—C11	115.79 (17)
C5—C4—H4A	108.4	C12—C11—C10	121.68 (18)
C3—C4—H4B	108.4	C12—C11—N2	115.89 (18)
C5—C4—H4B	108.4	C10—C11—N2	122.43 (16)
H4A—C4—H4B	107.4	C13—C12—C11	120.6 (2)
C6—C5—C4	115.93 (19)	C13—C12—H12	119.7
C6—C5—H5A	108.3	C11—C12—H12	119.7
C4—C5—H5A	108.3	C12—C13—C14	119.26 (19)
C6—C5—H5B	108.3	C12—C13—H13	120.4
C4—C5—H5B	108.3	C14—C13—H13	120.4
H5A—C5—H5B	107.4	C15—C14—C13	120.97 (19)
C5—C6—C7	115.73 (19)	C15—C14—H14	119.5
C5—C6—H6A	108.3	C13—C14—H14	119.5
C7—C6—H6A	108.3	C14—C15—C10	121.7 (2)
C5—C6—H6B	108.3	C14—C15—H15	119.1
C7—C6—H6B	108.3	C10—C15—H15	119.1
H6A—C6—H6B	107.4	N3—C16—C2	176.3 (2)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1···O1	0.86	1.89	2.593 (2)	138
C12—H12···O2	0.93	2.33	2.657 (3)	100
C15—H15···S1	0.93	2.44	3.171 (2)	135

	Cg1···Cg2	Cg1 to plane 2	Cg2 to plane 1	Offset
Cg1···Cg2i	3.7089 (12)	-3.5039 (9)	-3.5021 (9)	19.4
Cg1···Cg2ii	3.6170 (12)	3.4761 (9)	3.4878 (9)	16.0

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O1	0.86	1.89	2.593 (2)	138
C15—H15⋯S1	0.93	2.44	3.171 (2)	135