1-(4-Chloro-phen-yl)-3-(2-thienylcarbon-yl)thio-urea.

The title compound, C(12)H(9)ClN(2)OS(2), exists in the thio-amide form with an intra-molecular N-H⋯O hydrogen bond across the thio-urea and the carbonyl group. The dihedral angle between the rings is 10.36 (11)°. In the crystal structure, mol-ecules are linked into chains by weak inter-molecular C-H⋯Cl hydrogen-bonding inter-actions.

Related literature

For general background to the biological activity of thio­urea derivatives, see: Xu et al. (2004 ▶); Gu et al. (2007 ▶). For related structures, see: Saeed et al. (2008 ▶, 2009 ▶). For the cytotoxicity of anti­cancer drugs to normal cells in cancer therapy, see: Saeed et al. (2010 ▶).

Experimental

Crystal data

C12H9ClN2OS2

M = 296.78

Monoclinic,

a = 4.6552 (7) Å

b = 11.660 (2) Å

c = 23.630 (4) Å

β = 95.626 (2)°

V = 1276.4 (4) Å3

Z = 4

Mo Kα radiation

μ = 0.61 mm−1

T = 300 K

0.42 × 0.19 × 0.08 mm

Data collection

Bruker SMART 1000 CCD diffractometer

Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T min = 0.783, T max = 0.953

8549 measured reflections

3102 independent reflections

2578 reflections with I > 2σ(I)

R int = 0.019

Refinement

R[F 2 > 2σ(F 2)] = 0.038

wR(F 2) = 0.107

S = 1.07

3102 reflections

172 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.31 e Å−3

Δρmin = −0.20 e Å−3

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT and CrystalStructure (Rigaku/MSC and Rigaku, 2006 ▶); program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶) and DIAMOND (Brandenburg, 1998 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810013863/lx2142sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810013863/lx2142Isup2.hkl

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

C12H9ClN2OS2	F(000) = 608
Mr = 296.78	Dx = 1.544 Mg m−3
Monoclinic, P21/n	Melting point: 412 K
Hall symbol: -P 2yn	Mo Kα radiation, λ = 0.71073 Å
a = 4.6552 (7) Å	Cell parameters from 8801 reflections
b = 11.660 (2) Å	θ = 1.7–28.3°
c = 23.630 (4) Å	µ = 0.61 mm−1
β = 95.626 (2)°	T = 300 K
V = 1276.4 (4) Å3	Prism, yellow
Z = 4	0.42 × 0.19 × 0.08 mm

Bruker SMART 1000 CCD diffractometer	3102 independent reflections
Radiation source: fine-focus sealed tube	2578 reflections with I > 2σ(I)
graphite	Rint = 0.019
ω scan	θmax = 28.3°, θmin = 1.7°
Absorption correction: multi-scan (SADABS; Sheldrick, 1996)	h = −6→6
Tmin = 0.783, Tmax = 0.953	k = −9→15
8549 measured reflections	l = −30→31

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)] = 0.038	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.107	H atoms treated by a mixture of independent and constrained refinement
S = 1.07	w = 1/[σ2(Fo2) + (0.0546P)2 + 0.3548P] where P = (Fo2 + 2Fc2)/3
3102 reflections	(Δ/σ)max < 0.001
172 parameters	Δρmax = 0.31 e Å−3
0 restraints	Δρmin = −0.20 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 > 2sigma(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
Cl1	1.37357 (11)	0.14501 (5)	0.54454 (2)	0.06174 (17)
S1	0.42417 (13)	0.54355 (4)	0.38816 (3)	0.06558 (19)
S2	−0.38487 (12)	0.23708 (4)	0.20193 (2)	0.05870 (17)
O1	0.0745 (3)	0.22204 (11)	0.29637 (6)	0.0549 (3)
N1	0.4375 (3)	0.31315 (13)	0.37757 (6)	0.0426 (3)
H1N	0.357 (5)	0.2572 (18)	0.3578 (9)	0.053 (6)*
N2	0.0880 (3)	0.41119 (13)	0.32158 (7)	0.0446 (3)
H2N	0.001 (5)	0.475 (2)	0.3134 (10)	0.063 (7)*
C1	1.1034 (4)	0.19841 (16)	0.49542 (8)	0.0448 (4)
C2	0.9940 (4)	0.12913 (16)	0.45099 (8)	0.0470 (4)
H2	1.0655	0.0554	0.4470	0.056*
C3	0.7761 (4)	0.17123 (15)	0.41242 (7)	0.0446 (4)
H3	0.7010	0.1254	0.3823	0.053*
C4	0.6685 (4)	0.28161 (15)	0.41829 (7)	0.0395 (3)
C5	0.7819 (4)	0.34955 (16)	0.46329 (8)	0.0486 (4)
H5	0.7111	0.4233	0.4677	0.058*
C6	1.0007 (4)	0.30746 (17)	0.50170 (8)	0.0506 (4)
H6	1.0777	0.3531	0.5317	0.061*
C7	0.3216 (4)	0.41540 (14)	0.36378 (7)	0.0409 (4)
C8	−0.0182 (4)	0.32019 (15)	0.28912 (7)	0.0408 (4)
C9	−0.2510 (4)	0.34711 (15)	0.24497 (7)	0.0413 (4)
C10	−0.3865 (4)	0.44880 (17)	0.22982 (8)	0.0499 (4)
H10	−0.3439	0.5183	0.2481	0.060*
C11	−0.5988 (5)	0.43535 (18)	0.18316 (9)	0.0574 (5)
H11	−0.7109	0.4952	0.1671	0.069*
C12	−0.6202 (5)	0.32616 (19)	0.16464 (9)	0.0586 (5)
H12	−0.7503	0.3022	0.1346	0.070*

	U11	U22	U33	U12	U13	U23
Cl1	0.0533 (3)	0.0688 (3)	0.0585 (3)	−0.0017 (2)	−0.0177 (2)	0.0113 (2)
S1	0.0745 (4)	0.0364 (2)	0.0783 (4)	−0.0039 (2)	−0.0311 (3)	−0.0049 (2)
S2	0.0706 (3)	0.0434 (3)	0.0563 (3)	0.0030 (2)	−0.0228 (2)	−0.0074 (2)
O1	0.0672 (9)	0.0381 (6)	0.0547 (8)	0.0023 (6)	−0.0187 (6)	−0.0028 (6)
N1	0.0463 (8)	0.0358 (7)	0.0429 (8)	−0.0042 (6)	−0.0088 (6)	−0.0016 (6)
N2	0.0469 (8)	0.0372 (7)	0.0466 (8)	0.0002 (6)	−0.0105 (6)	−0.0020 (6)
C1	0.0384 (8)	0.0518 (10)	0.0427 (9)	−0.0060 (7)	−0.0035 (7)	0.0076 (7)
C2	0.0494 (10)	0.0429 (9)	0.0473 (9)	0.0012 (8)	−0.0023 (7)	0.0025 (7)
C3	0.0491 (9)	0.0403 (9)	0.0423 (9)	−0.0046 (7)	−0.0060 (7)	−0.0026 (7)
C4	0.0387 (8)	0.0392 (8)	0.0394 (8)	−0.0047 (6)	−0.0026 (6)	0.0029 (7)
C5	0.0552 (10)	0.0416 (9)	0.0465 (9)	−0.0005 (8)	−0.0075 (8)	−0.0035 (7)
C6	0.0526 (10)	0.0501 (10)	0.0460 (9)	−0.0084 (8)	−0.0113 (8)	−0.0045 (8)
C7	0.0418 (8)	0.0395 (8)	0.0401 (8)	−0.0048 (7)	−0.0030 (6)	−0.0010 (7)
C8	0.0428 (8)	0.0395 (8)	0.0388 (8)	−0.0031 (7)	−0.0020 (6)	0.0002 (7)
C9	0.0436 (8)	0.0394 (9)	0.0392 (8)	−0.0041 (7)	−0.0042 (6)	0.0001 (7)
C10	0.0528 (10)	0.0419 (10)	0.0519 (10)	0.0004 (8)	−0.0098 (8)	0.0005 (8)
C11	0.0578 (11)	0.0509 (11)	0.0595 (12)	0.0041 (9)	−0.0146 (9)	0.0077 (9)
C12	0.0620 (12)	0.0570 (12)	0.0514 (10)	−0.0013 (9)	−0.0214 (9)	0.0007 (9)

Cl1—C1	1.7408 (18)	C2—H2	0.9300
S1—C7	1.6548 (17)	C3—C4	1.393 (2)
S2—C12	1.693 (2)	C3—H3	0.9300
S2—C9	1.7158 (17)	C4—C5	1.388 (2)
O1—C8	1.229 (2)	C5—C6	1.386 (3)
N1—C7	1.336 (2)	C5—H5	0.9300
N1—C4	1.419 (2)	C6—H6	0.9300
N1—H1N	0.87 (2)	C8—C9	1.463 (2)
N2—C8	1.373 (2)	C9—C10	1.374 (2)
N2—C7	1.402 (2)	C10—C11	1.415 (3)
N2—H2N	0.86 (2)	C10—H10	0.9300
C1—C6	1.372 (3)	C11—C12	1.347 (3)
C1—C2	1.382 (3)	C11—H11	0.9300
C2—C3	1.385 (2)	C12—H12	0.9300
C12—S2—C9	91.64 (10)	C1—C6—C5	119.94 (17)
C7—N1—C4	131.12 (15)	C1—C6—H6	120.0
C7—N1—H1N	113.5 (14)	C5—C6—H6	120.0
C4—N1—H1N	115.4 (14)	N1—C7—N2	114.12 (15)
C8—N2—C7	129.51 (16)	N1—C7—S1	128.69 (13)
C8—N2—H2N	113.9 (16)	N2—C7—S1	117.15 (13)
C7—N2—H2N	116.5 (16)	O1—C8—N2	122.64 (16)
C6—C1—C2	121.18 (16)	O1—C8—C9	121.65 (16)
C6—C1—Cl1	119.75 (14)	N2—C8—C9	115.71 (15)
C2—C1—Cl1	119.06 (15)	C10—C9—C8	131.32 (16)
C1—C2—C3	118.96 (17)	C10—C9—S2	111.10 (13)
C1—C2—H2	120.5	C8—C9—S2	117.57 (13)
C3—C2—H2	120.5	C9—C10—C11	112.03 (17)
C2—C3—C4	120.61 (16)	C9—C10—H10	124.0
C2—C3—H3	119.7	C11—C10—H10	124.0
C4—C3—H3	119.7	C12—C11—C10	112.44 (18)
C5—C4—C3	119.35 (16)	C12—C11—H11	123.8
C5—C4—N1	125.26 (16)	C10—C11—H11	123.8
C3—C4—N1	115.33 (15)	C11—C12—S2	112.79 (15)
C6—C5—C4	119.96 (18)	C11—C12—H12	123.6
C6—C5—H5	120.0	S2—C12—H12	123.6
C4—C5—H5	120.0

D—H···A	D—H	H···A	D···A	D—H···A
N1—H1N···O1	0.87 (2)	1.91 (2)	2.651 (2)	143 (2)
C12—H12···Cl1i	0.93	2.69	3.523 (2)	149

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1N⋯O1	0.87 (2)	1.91 (2)	2.651 (2)	143 (2)
C12—H12⋯Cl1i	0.93	2.69	3.523 (2)	149

Symmetry code: (i) .