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

The title compound, C(12)H(9)BrN(2)OS(2), consists of two planar parts, viz. the thio-phene ring including all substituents (r.m.s. deviation 0.007 Å) and the benzene ring including the respective substituents as well as the thione group (r.m.s. deviation 0.05 Å). The inter-planar angle is 18.84 (6)°. An intra-molecular C(phen-yl)-N-H⋯OC hydrogen bond is observed. The three-dimensional packing involves three types of inter-actions, viz. N-H⋯S, C-H⋯S (× 2) and Br⋯S [3.6924 (6) Å].

Related literature

For general background to the chemistry of thio­urea derivatives, see: Choi et al. (2008 ▶); Jones et al. (2008 ▶); Su et al. (2006 ▶). For related structures, see: Saeed et al. (2008a ▶,b ▶,c ▶); Yunus et al. (2008 ▶). For the cytotoxicity and genotoxicity of anticancer drugs to normal cells in cancer therapy, see: Aydemir & Bilaloglu (2003 ▶).

Experimental

Crystal data

C12H9BrN2OS2

M = 341.24

Monoclinic,

a = 13.1483 (6) Å

b = 4.4263 (2) Å

c = 22.671 (1) Å

β = 90.412 (5)°

V = 1319.4 (1) Å3

Z = 4

Cu Kα radiation

μ = 7.12 mm−1

T = 100 K

0.15 × 0.05 × 0.02 mm

Data collection

Oxford Diffraction Xcalibur Nova A diffractometer

Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009 ▶) T min = 0.558, T max = 1.000

20285 measured reflections

2712 independent reflections

2438 reflections with I > 2σ(I)

R int = 0.040

Refinement

R[F 2 > 2σ(F 2)] = 0.025

wR(F 2) = 0.067

S = 1.06

2712 reflections

171 parameters

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 0.42 e Å−3

Δρmin = −0.36 e Å−3

Data collection: CrysAlis Pro (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis Pro; data reduction: CrysAlis Pro; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Siemens, 1994 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809038537/im2139sup1.cif

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809038537/im2139Isup2.hkl

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

C12H9BrN2OS2	F(000) = 680
Mr = 341.24	Dx = 1.718 Mg m−3
Monoclinic, P21/n	Melting point: 389 K
Hall symbol: -P 2yn	Cu Kα radiation, λ = 1.54184 Å
a = 13.1483 (6) Å	Cell parameters from 12273 reflections
b = 4.4263 (2) Å	θ = 3.4–75.7°
c = 22.671 (1) Å	µ = 7.12 mm−1
β = 90.412 (5)°	T = 100 K
V = 1319.4 (1) Å3	Needle, colourless
Z = 4	0.15 × 0.05 × 0.02 mm

Oxford Diffraction Xcalibur Nova A diffractometer	2712 independent reflections
Radiation source: Nova (Cu) X-ray Source	2438 reflections with I > 2σ(I)
mirror	Rint = 0.040
Detector resolution: 10.3543 pixels mm-1	θmax = 75.9°, θmin = 3.9°
ω scans	h = −16→16
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2009)	k = −5→4
Tmin = 0.558, Tmax = 1.000	l = −28→27
20285 measured 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)] = 0.025	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.067	H atoms treated by a mixture of independent and constrained refinement
S = 1.06	w = 1/[σ2(Fo2) + (0.0399P)2 + 0.686P] where P = (Fo2 + 2Fc2)/3
2712 reflections	(Δ/σ)max = 0.002
171 parameters	Δρmax = 0.42 e Å−3
0 restraints	Δρmin = −0.36 e Å−3

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.Short contact:3.6924 (0.0006) S1 - Br_$3 165.89 (0.07) C1 - S1 - Br_$3 90.51 (0.06) S1 - Br_$3 - C10_$3 Operator for generating equivalent atoms: $3 - x + 1/2, y - 3/2, -z + 1/2Least-squares planes (x,y,z in crystal coordinates) and deviations from them (* indicates atom used to define plane)- 2.2923 (0.0090) x + 3.4843 (0.0018) y + 13.4394 (0.0126) z = 3.7714 (0.0071)* -0.0064 (0.0017) C1 * -0.0022 (0.0013) C2 * -0.0022 (0.0014) C3 * 0.0106 (0.0014) C4 * -0.0078 (0.0010) S1 * 0.0079 (0.0011) C5Rms deviation of fitted atoms = 0.0069- 5.4364 (0.0073) x + 3.6780 (0.0010) y + 8.5062 (0.0060) z = 1.0213 (0.0056)Angle to previous plane (with approximate e.s.d.) = 18.84 (0.06)* -0.0768 (0.0015) C6 * 0.0657 (0.0011) S2 * 0.0104 (0.0018) C7 * 0.0477 (0.0017) C8 * 0.0508 (0.0017) C9 * 0.0153 (0.0017) C10 * 0.0055 (0.0018) C11 * 0.0033 (0.0020) C12 * -0.0663 (0.0010) Br * -0.0558 (0.0015) N2 - 0.2202 (0.0028) C5 - 0.1410 (0.0028) O -0.2122 (0.0021) N1Rms deviation of fitted atoms = 0.0479

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
Br	0.629471 (15)	0.87392 (5)	0.136702 (8)	0.02773 (9)
S1	0.12627 (4)	−0.47575 (13)	0.42493 (2)	0.03066 (13)
S2	0.57481 (4)	0.15778 (13)	0.42693 (2)	0.02881 (13)
O	0.27346 (11)	−0.1628 (4)	0.34866 (6)	0.0306 (3)
N1	0.40397 (12)	−0.1458 (4)	0.41634 (7)	0.0213 (3)
H01	0.4194 (19)	−0.180 (6)	0.4521 (12)	0.031 (7)*
N2	0.44284 (13)	0.1420 (4)	0.33512 (7)	0.0238 (4)
H02	0.385 (2)	0.075 (6)	0.3245 (11)	0.032 (7)*
C1	0.25426 (14)	−0.4373 (5)	0.43690 (8)	0.0228 (4)
C2	0.28750 (14)	−0.6036 (4)	0.48600 (8)	0.0191 (4)
H2	0.3558	−0.6113	0.4998	0.023*
C3	0.20512 (17)	−0.7586 (5)	0.51212 (9)	0.0303 (4)
H3	0.2122	−0.8857	0.5457	0.036*
C4	0.11538 (17)	−0.7072 (5)	0.48445 (11)	0.0340 (5)
H4	0.0527	−0.7916	0.4969	0.041*
C5	0.31026 (14)	−0.2406 (5)	0.39652 (8)	0.0226 (4)
C6	0.47172 (14)	0.0541 (5)	0.38914 (8)	0.0215 (4)
C7	0.49109 (15)	0.3288 (4)	0.29299 (8)	0.0213 (4)
C8	0.43466 (15)	0.3754 (5)	0.24114 (9)	0.0251 (4)
H8	0.3683	0.2922	0.2375	0.030*
C9	0.47486 (15)	0.5415 (5)	0.19539 (9)	0.0268 (4)
H9	0.4365	0.5732	0.1603	0.032*
C10	0.57114 (15)	0.6608 (4)	0.20115 (8)	0.0228 (4)
C11	0.62707 (15)	0.6225 (5)	0.25232 (9)	0.0279 (4)
H11	0.6928	0.7100	0.2559	0.033*
C12	0.58713 (15)	0.4557 (5)	0.29867 (9)	0.0293 (4)
H12	0.6254	0.4288	0.3340	0.035*

	U11	U22	U33	U12	U13	U23
Br	0.02733 (13)	0.03447 (14)	0.02145 (12)	0.00217 (8)	0.00351 (8)	0.00748 (8)
S1	0.0204 (2)	0.0323 (3)	0.0393 (3)	−0.0031 (2)	−0.00143 (19)	−0.0057 (2)
S2	0.0253 (2)	0.0430 (3)	0.0181 (2)	−0.0118 (2)	−0.00757 (18)	0.00732 (19)
O	0.0251 (7)	0.0443 (9)	0.0222 (7)	−0.0074 (6)	−0.0074 (6)	0.0054 (6)
N1	0.0211 (8)	0.0283 (9)	0.0145 (8)	−0.0019 (6)	−0.0039 (6)	0.0029 (6)
N2	0.0208 (8)	0.0319 (9)	0.0187 (8)	−0.0042 (7)	−0.0045 (6)	0.0038 (7)
C1	0.0193 (8)	0.0278 (10)	0.0212 (9)	−0.0023 (8)	0.0005 (7)	−0.0055 (8)
C2	0.0217 (9)	0.0198 (9)	0.0159 (8)	−0.0038 (7)	0.0010 (7)	−0.0037 (7)
C3	0.0391 (11)	0.0255 (10)	0.0266 (10)	−0.0025 (9)	0.0095 (8)	−0.0036 (9)
C4	0.0286 (10)	0.0260 (11)	0.0477 (13)	−0.0049 (9)	0.0173 (9)	−0.0085 (10)
C5	0.0207 (8)	0.0272 (10)	0.0199 (9)	−0.0008 (8)	−0.0020 (7)	−0.0027 (8)
C6	0.0213 (8)	0.0258 (10)	0.0174 (8)	0.0004 (7)	−0.0024 (7)	0.0002 (7)
C7	0.0230 (9)	0.0247 (10)	0.0162 (8)	0.0002 (7)	−0.0009 (7)	0.0014 (7)
C8	0.0223 (9)	0.0320 (11)	0.0210 (9)	−0.0031 (8)	−0.0047 (7)	0.0021 (8)
C9	0.0290 (10)	0.0331 (11)	0.0184 (9)	0.0002 (9)	−0.0053 (7)	0.0041 (8)
C10	0.0264 (9)	0.0232 (10)	0.0190 (9)	0.0034 (7)	0.0027 (7)	0.0035 (7)
C11	0.0222 (9)	0.0376 (12)	0.0238 (10)	−0.0027 (8)	−0.0029 (8)	0.0053 (8)
C12	0.0253 (10)	0.0411 (12)	0.0212 (9)	−0.0027 (9)	−0.0052 (7)	0.0077 (9)

Br—C10	1.9050 (19)	C7—C12	1.387 (3)
S1—C4	1.701 (3)	C7—C8	1.401 (3)
S1—C1	1.7111 (19)	C8—C9	1.379 (3)
S2—C6	1.6629 (19)	C9—C10	1.377 (3)
O—C5	1.234 (2)	C10—C11	1.380 (3)
N1—C5	1.374 (2)	C11—C12	1.390 (3)
N1—C6	1.402 (3)	N1—H01	0.85 (3)
N2—C6	1.338 (2)	N2—H02	0.85 (3)
N2—C7	1.417 (3)	C2—H2	0.9500
C1—C2	1.402 (3)	C3—H3	0.9500
C1—C5	1.465 (3)	C4—H4	0.9500
C2—C3	1.415 (3)	C8—H8	0.9500
C3—C4	1.352 (3)	C9—H9	0.9500
C4—S1—C1	91.28 (10)	C11—C10—Br	119.39 (15)
C5—N1—C6	128.33 (16)	C10—C11—C12	119.92 (19)
C6—N2—C7	131.42 (17)	C7—C12—C11	119.56 (18)
C2—C1—C5	130.75 (17)	C5—N1—H01	117.8 (18)
C2—C1—S1	111.98 (14)	C6—N1—H01	112.6 (18)
C5—C1—S1	117.26 (14)	C6—N2—H02	113.9 (18)
C1—C2—C3	110.59 (17)	C7—N2—H02	114.7 (18)
C4—C3—C2	113.1 (2)	C1—C2—H2	124.7
C3—C4—S1	113.04 (16)	C3—C2—H2	124.7
O—C5—N1	123.18 (18)	C4—C3—H3	123.5
O—C5—C1	121.29 (17)	C2—C3—H3	123.5
N1—C5—C1	115.51 (16)	C3—C4—H4	123.5
N2—C6—N1	114.16 (16)	S1—C4—H4	123.5
N2—C6—S2	128.06 (16)	C9—C8—H8	119.8
N1—C6—S2	117.77 (13)	C7—C8—H8	119.8
C12—C7—C8	119.64 (18)	C10—C9—H9	120.3
C12—C7—N2	125.84 (17)	C8—C9—H9	120.3
C8—C7—N2	114.50 (17)	C10—C11—H11	120.0
C9—C8—C7	120.39 (18)	C12—C11—H11	120.0
C10—C9—C8	119.34 (18)	C7—C12—H12	120.2
C9—C10—C11	121.11 (18)	C11—C12—H12	120.2
C9—C10—Br	119.48 (15)
C4—S1—C1—C2	0.46 (16)	C5—N1—C6—N2	−5.5 (3)
C4—S1—C1—C5	−178.78 (16)	C5—N1—C6—S2	173.38 (16)
C5—C1—C2—C3	179.2 (2)	C6—N2—C7—C12	3.5 (4)
S1—C1—C2—C3	0.1 (2)	C6—N2—C7—C8	−178.4 (2)
C1—C2—C3—C4	−0.8 (3)	C12—C7—C8—C9	1.3 (3)
C2—C3—C4—S1	1.1 (2)	N2—C7—C8—C9	−177.00 (19)
C1—S1—C4—C3	−0.92 (18)	C7—C8—C9—C10	0.1 (3)
C6—N1—C5—O	2.2 (3)	C8—C9—C10—C11	−1.4 (3)
C6—N1—C5—C1	−176.30 (18)	C8—C9—C10—Br	177.04 (16)
C2—C1—C5—O	164.5 (2)	C9—C10—C11—C12	1.4 (3)
S1—C1—C5—O	−16.4 (3)	Br—C10—C11—C12	−177.09 (17)
C2—C1—C5—N1	−17.0 (3)	C8—C7—C12—C11	−1.3 (3)
S1—C1—C5—N1	162.10 (14)	N2—C7—C12—C11	176.8 (2)
C7—N2—C6—N1	−177.11 (19)	C10—C11—C12—C7	0.0 (3)
C7—N2—C6—S2	4.2 (3)

D—H···A	D—H	H···A	D···A	D—H···A
N1—H01···S2i	0.85 (3)	2.74 (3)	3.5625 (16)	163 (2)
N2—H02···O	0.85 (3)	1.89 (3)	2.624 (2)	144 (2)
C9—H9···S1ii	0.95	2.89	3.704 (2)	144
C2—H2···S2i	0.95	2.76	3.3193 (18)	119

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H01⋯S2i	0.85 (3)	2.74 (3)	3.5625 (16)	163 (2)
N2—H02⋯O	0.85 (3)	1.89 (3)	2.624 (2)	144 (2)
C9—H9⋯S1ii	0.95	2.89	3.704 (2)	144
C2—H2⋯S2i	0.95	2.76	3.3193 (18)	119

Symmetry codes: (i) ; (ii) .