N-(4-Bromo-butano-yl)-N'-phen-ylthio-urea.

The asymmetric unit of the title compound, C(11)H(13)Br(1)N(2)O(1)S(1), consists of two independent mol-ecules, which are linked by N-H⋯O hydrogen bonds, forming a dimer. Both mol-ecules maintain the trans--cis configuration with respect to the position of the butanoyl groups and benzene rings against the thiono group across the C-N bonds. The mol-ecule is stabilized by intra-molecular N-H⋯O hydrogen bonds. Inter-molecular N-H⋯S, C-H⋯S and C-H⋯π inter-actions also occur.

Related literature

For related structures of halocarbonyl thio­urea derivatives, see: Othman et al. (2010 ▶); Yamin et al. (2011 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C11H13BrN2OS

M = 301.20

Monoclinic,

a = 14.689 (3) Å

b = 10.349 (2) Å

c = 18.249 (4) Å

β = 111.220 (5)°

V = 2586.0 (10) Å3

Z = 8

Mo Kα radiation

μ = 3.32 mm−1

T = 298 K

0.50 × 0.33 × 0.10 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2000 ▶) T min = 0.287, T max = 0.732

15722 measured reflections

5077 independent reflections

3076 reflections with I > 2/s(I)

R int = 0.048

Refinement

R[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 0.177

S = 1.01

5077 reflections

289 parameters

H-atom parameters constrained

Δρmax = 0.89 e Å−3

Δρmin = −0.75 e Å−3

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL, PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2009) ▶.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811021684/dn2691sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811021684/dn2691Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811021684/dn2691Isup3.cml

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

C11H13BrN2OS	F(000) = 1216
Mr = 301.20	Dx = 1.547 Mg m−3
Monoclinic, P21/c	Melting point = 392.3–393.2 K
Hall symbol: -P 2ybc	Mo Kα radiation, λ = 0.71073 Å
a = 14.689 (3) Å	Cell parameters from 2780 reflections
b = 10.349 (2) Å	θ = 1.5–26.0°
c = 18.249 (4) Å	µ = 3.32 mm−1
β = 111.220 (5)°	T = 298 K
V = 2586.0 (10) Å3	Block, colourless
Z = 8	0.50 × 0.33 × 0.10 mm

Bruker SMART APEX CCD area-detector diffractometer	5077 independent reflections
Radiation source: fine-focus sealed tube	3076 reflections with I > 2/s(I)
graphite	Rint = 0.048
Detector resolution: 83.66 pixels mm-1	θmax = 26.0°, θmin = 1.5°
ω scan	h = −17→18
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −12→9
Tmin = 0.287, Tmax = 0.732	l = −21→22
15722 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)] = 0.058	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.177	H-atom parameters constrained
S = 1.01	w = 1/[σ2(Fo2) + (0.0843P)2 + 2.7585P] where P = (Fo2 + 2Fc2)/3
5077 reflections	(Δ/σ)max = 0.001
289 parameters	Δρmax = 0.89 e Å−3
0 restraints	Δρmin = −0.75 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.

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
Br1	1.00981 (7)	0.72786 (12)	1.00605 (6)	0.1327 (4)
Br2	0.28595 (5)	0.69236 (7)	0.28367 (4)	0.0784 (3)
S1	0.48380 (9)	0.47455 (14)	0.83458 (8)	0.0528 (4)
S2	0.74841 (9)	1.02020 (13)	0.52423 (8)	0.0513 (3)
O1	0.7046 (3)	0.6521 (4)	0.7416 (2)	0.0615 (10)
O2	0.5743 (3)	0.6931 (3)	0.5762 (2)	0.0555 (9)
N1	0.6510 (3)	0.5574 (4)	0.8311 (2)	0.0458 (10)
H1	0.6702	0.5361	0.8799	0.055*
N2	0.5208 (3)	0.5717 (4)	0.7131 (2)	0.0478 (10)
H2	0.5610	0.6068	0.6946	0.057*
N3	0.6000 (3)	0.8661 (4)	0.5094 (2)	0.0427 (9)
H3	0.5736	0.9093	0.4666	0.051*
N4	0.7312 (3)	0.8488 (4)	0.6266 (2)	0.0491 (10)
H4	0.6998	0.7869	0.6382	0.059*
C1	1.0005 (4)	0.6481 (8)	0.9059 (4)	0.091 (2)
H1A	1.0458	0.6906	0.8861	0.109*
H1B	1.0193	0.5579	0.9148	0.109*
C2	0.8995 (4)	0.6569 (7)	0.8455 (4)	0.0767 (19)
H2A	0.8814	0.7474	0.8370	0.092*
H2B	0.9003	0.6225	0.7963	0.092*
C3	0.8241 (4)	0.5886 (6)	0.8656 (3)	0.0588 (14)
H3A	0.8255	0.6194	0.9162	0.071*
H3B	0.8399	0.4972	0.8709	0.071*
C4	0.7220 (4)	0.6051 (5)	0.8060 (3)	0.0486 (12)
C5	0.5530 (3)	0.5391 (4)	0.7884 (3)	0.0407 (11)
C6	0.4217 (3)	0.5511 (5)	0.6608 (3)	0.0443 (11)
C7	0.3889 (4)	0.4292 (6)	0.6373 (3)	0.0623 (15)
H7	0.4297	0.3584	0.6562	0.075*
C8	0.2944 (5)	0.4120 (7)	0.5851 (4)	0.0777 (19)
H8	0.2713	0.3292	0.5688	0.093*
C9	0.2350 (4)	0.5158 (8)	0.5576 (4)	0.080 (2)
H9	0.1712	0.5036	0.5230	0.096*
C10	0.2687 (4)	0.6376 (7)	0.5803 (4)	0.0740 (18)
H10	0.2281	0.7084	0.5609	0.089*
C11	0.3631 (4)	0.6559 (6)	0.6324 (3)	0.0576 (14)
H11	0.3866	0.7388	0.6479	0.069*
C12	0.2997 (4)	0.6205 (6)	0.3859 (3)	0.0624 (15)
H12A	0.2589	0.6690	0.4076	0.075*
H12B	0.2772	0.5317	0.3792	0.075*
C13	0.4040 (4)	0.6247 (5)	0.4427 (3)	0.0510 (12)
H13A	0.4079	0.5829	0.4914	0.061*
H13B	0.4447	0.5762	0.4208	0.061*
C14	0.4432 (4)	0.7593 (5)	0.4606 (3)	0.0544 (13)
H14A	0.3995	0.8094	0.4785	0.065*
H14B	0.4437	0.7986	0.4124	0.065*
C15	0.5449 (3)	0.7663 (5)	0.5219 (3)	0.0442 (11)
C16	0.6924 (3)	0.9049 (4)	0.5572 (3)	0.0423 (11)
C17	0.8234 (4)	0.8868 (5)	0.6832 (3)	0.0497 (12)
C18	0.9079 (4)	0.8368 (7)	0.6801 (4)	0.0709 (17)
H18	0.9066	0.7786	0.6409	0.085*
C19	0.9966 (5)	0.8749 (9)	0.7373 (5)	0.093 (2)
H19	1.0549	0.8426	0.7356	0.112*
C20	0.9985 (6)	0.9573 (9)	0.7942 (5)	0.100 (3)
H20	1.0579	0.9810	0.8321	0.120*
C21	0.9142 (6)	1.0065 (7)	0.7972 (5)	0.095 (2)
H21	0.9164	1.0643	0.8368	0.114*
C22	0.8253 (5)	0.9712 (6)	0.7417 (4)	0.0694 (16)
H22	0.7675	1.0042	0.7439	0.083*

	U11	U22	U33	U12	U13	U23
Br1	0.0786 (6)	0.1732 (10)	0.1102 (7)	−0.0418 (6)	−0.0091 (5)	−0.0171 (6)
Br2	0.0770 (5)	0.0753 (5)	0.0611 (4)	0.0005 (3)	−0.0013 (3)	−0.0011 (3)
S1	0.0424 (7)	0.0709 (9)	0.0440 (7)	−0.0065 (6)	0.0144 (6)	0.0010 (6)
S2	0.0425 (7)	0.0632 (8)	0.0445 (7)	−0.0108 (6)	0.0111 (6)	0.0055 (6)
O1	0.044 (2)	0.079 (3)	0.053 (2)	−0.0140 (18)	0.0074 (17)	0.0128 (19)
O2	0.049 (2)	0.054 (2)	0.051 (2)	−0.0114 (17)	0.0036 (17)	0.0105 (17)
N1	0.036 (2)	0.060 (3)	0.036 (2)	−0.0008 (18)	0.0054 (18)	0.0018 (18)
N2	0.038 (2)	0.060 (3)	0.040 (2)	−0.0077 (19)	0.0073 (18)	0.0072 (19)
N3	0.035 (2)	0.052 (2)	0.035 (2)	−0.0029 (18)	0.0048 (17)	0.0031 (17)
N4	0.036 (2)	0.059 (3)	0.043 (2)	−0.0082 (19)	0.0032 (18)	0.0071 (19)
C1	0.041 (3)	0.132 (6)	0.096 (5)	0.011 (4)	0.021 (4)	0.041 (5)
C2	0.041 (3)	0.121 (6)	0.063 (4)	0.005 (3)	0.013 (3)	0.024 (4)
C3	0.046 (3)	0.070 (4)	0.052 (3)	−0.007 (3)	0.008 (3)	0.006 (3)
C4	0.041 (3)	0.057 (3)	0.043 (3)	−0.008 (2)	0.009 (2)	−0.002 (2)
C5	0.041 (3)	0.039 (3)	0.040 (3)	0.002 (2)	0.012 (2)	−0.002 (2)
C6	0.034 (2)	0.058 (3)	0.036 (2)	−0.006 (2)	0.007 (2)	0.001 (2)
C7	0.057 (3)	0.058 (3)	0.060 (3)	−0.006 (3)	0.006 (3)	0.006 (3)
C8	0.068 (4)	0.080 (5)	0.071 (4)	−0.030 (4)	0.008 (3)	−0.003 (3)
C9	0.039 (3)	0.125 (6)	0.059 (4)	−0.017 (4)	−0.002 (3)	0.012 (4)
C10	0.042 (3)	0.091 (5)	0.079 (4)	0.010 (3)	0.010 (3)	0.015 (4)
C11	0.051 (3)	0.059 (3)	0.061 (3)	0.003 (3)	0.018 (3)	0.001 (3)
C12	0.051 (3)	0.066 (4)	0.061 (3)	−0.017 (3)	0.010 (3)	−0.005 (3)
C13	0.044 (3)	0.051 (3)	0.051 (3)	−0.007 (2)	0.009 (2)	0.000 (2)
C14	0.044 (3)	0.048 (3)	0.060 (3)	0.001 (2)	0.006 (3)	0.004 (2)
C15	0.039 (3)	0.045 (3)	0.046 (3)	−0.006 (2)	0.013 (2)	−0.005 (2)
C16	0.038 (3)	0.046 (3)	0.042 (3)	0.001 (2)	0.012 (2)	−0.004 (2)
C17	0.043 (3)	0.051 (3)	0.045 (3)	−0.004 (2)	0.004 (2)	0.012 (2)
C18	0.047 (3)	0.096 (5)	0.065 (4)	−0.002 (3)	0.014 (3)	0.007 (3)
C19	0.043 (4)	0.128 (7)	0.095 (6)	−0.002 (4)	0.008 (4)	0.031 (5)
C20	0.068 (5)	0.108 (6)	0.084 (6)	−0.030 (5)	−0.020 (4)	0.015 (5)
C21	0.090 (6)	0.077 (5)	0.080 (5)	−0.014 (4)	−0.014 (4)	−0.008 (4)
C22	0.065 (4)	0.057 (4)	0.068 (4)	−0.002 (3)	0.002 (3)	−0.001 (3)

Br1—C1	1.964 (8)	C7—C8	1.383 (8)
Br2—C12	1.950 (6)	C7—H7	0.9300
S1—C5	1.676 (5)	C8—C9	1.360 (9)
S2—C16	1.680 (5)	C8—H8	0.9300
O1—C4	1.211 (6)	C9—C10	1.363 (9)
O2—C15	1.196 (6)	C9—H9	0.9300
N1—C4	1.373 (6)	C10—C11	1.382 (8)
N1—C5	1.380 (6)	C10—H10	0.9300
N1—H1	0.8600	C11—H11	0.9300
N2—C5	1.325 (6)	C12—C13	1.508 (7)
N2—C6	1.437 (6)	C12—H12A	0.9700
N2—H2	0.8600	C12—H12B	0.9700
N3—C16	1.381 (6)	C13—C14	1.497 (7)
N3—C15	1.381 (6)	C13—H13A	0.9700
N3—H3	0.8600	C13—H13B	0.9700
N4—C16	1.321 (6)	C14—C15	1.510 (7)
N4—C17	1.429 (6)	C14—H14A	0.9700
N4—H4	0.8600	C14—H14B	0.9700
C1—C2	1.497 (8)	C17—C18	1.364 (8)
C1—H1A	0.9700	C17—C22	1.372 (8)
C1—H1B	0.9700	C18—C19	1.399 (9)
C2—C3	1.467 (8)	C18—H18	0.9300
C2—H2A	0.9700	C19—C20	1.337 (12)
C2—H2B	0.9700	C19—H19	0.9300
C3—C4	1.510 (7)	C20—C21	1.357 (11)
C3—H3A	0.9700	C20—H20	0.9300
C3—H3B	0.9700	C21—C22	1.381 (9)
C6—C7	1.362 (7)	C21—H21	0.9300
C6—C11	1.365 (7)	C22—H22	0.9300
C4—N1—C5	128.6 (4)	C9—C10—C11	120.0 (6)
C4—N1—H1	115.7	C9—C10—H10	120.0
C5—N1—H1	115.7	C11—C10—H10	120.0
C5—N2—C6	123.1 (4)	C6—C11—C10	119.4 (6)
C5—N2—H2	118.4	C6—C11—H11	120.3
C6—N2—H2	118.4	C10—C11—H11	120.3
C16—N3—C15	127.8 (4)	C13—C12—Br2	112.0 (4)
C16—N3—H3	116.1	C13—C12—H12A	109.2
C15—N3—H3	116.1	Br2—C12—H12A	109.2
C16—N4—C17	122.6 (4)	C13—C12—H12B	109.2
C16—N4—H4	118.7	Br2—C12—H12B	109.2
C17—N4—H4	118.7	H12A—C12—H12B	107.9
C2—C1—Br1	112.1 (5)	C14—C13—C12	113.0 (4)
C2—C1—H1A	109.2	C14—C13—H13A	109.0
Br1—C1—H1A	109.2	C12—C13—H13A	109.0
C2—C1—H1B	109.2	C14—C13—H13B	109.0
Br1—C1—H1B	109.2	C12—C13—H13B	109.0
H1A—C1—H1B	107.9	H13A—C13—H13B	107.8
C3—C2—C1	115.0 (5)	C13—C14—C15	113.9 (4)
C3—C2—H2A	108.5	C13—C14—H14A	108.8
C1—C2—H2A	108.5	C15—C14—H14A	108.8
C3—C2—H2B	108.5	C13—C14—H14B	108.8
C1—C2—H2B	108.5	C15—C14—H14B	108.8
H2A—C2—H2B	107.5	H14A—C14—H14B	107.7
C2—C3—C4	114.1 (5)	O2—C15—N3	123.6 (4)
C2—C3—H3A	108.7	O2—C15—C14	123.2 (4)
C4—C3—H3A	108.7	N3—C15—C14	113.2 (4)
C2—C3—H3B	108.7	N4—C16—N3	117.6 (4)
C4—C3—H3B	108.7	N4—C16—S2	123.9 (4)
H3A—C3—H3B	107.6	N3—C16—S2	118.5 (3)
O1—C4—N1	123.3 (5)	C18—C17—C22	120.7 (5)
O1—C4—C3	123.4 (5)	C18—C17—N4	120.3 (5)
N1—C4—C3	113.3 (4)	C22—C17—N4	118.9 (5)
N2—C5—N1	117.3 (4)	C17—C18—C19	118.6 (7)
N2—C5—S1	124.6 (4)	C17—C18—H18	120.7
N1—C5—S1	118.0 (3)	C19—C18—H18	120.7
C7—C6—C11	120.9 (5)	C20—C19—C18	120.7 (7)
C7—C6—N2	120.2 (5)	C20—C19—H19	119.7
C11—C6—N2	118.8 (5)	C18—C19—H19	119.7
C6—C7—C8	119.3 (6)	C19—C20—C21	120.5 (7)
C6—C7—H7	120.4	C19—C20—H20	119.7
C8—C7—H7	120.4	C21—C20—H20	119.7
C9—C8—C7	120.2 (6)	C20—C21—C22	120.4 (7)
C9—C8—H8	119.9	C20—C21—H21	119.8
C7—C8—H8	119.9	C22—C21—H21	119.8
C8—C9—C10	120.3 (6)	C17—C22—C21	119.1 (7)
C8—C9—H9	119.8	C17—C22—H22	120.5
C10—C9—H9	119.8	C21—C22—H22	120.5
Br1—C1—C2—C3	−62.8 (8)	Br2—C12—C13—C14	62.5 (6)
C1—C2—C3—C4	176.7 (6)	C12—C13—C14—C15	175.7 (5)
C5—N1—C4—O1	8.4 (8)	C16—N3—C15—O2	−4.7 (8)
C5—N1—C4—C3	−169.5 (5)	C16—N3—C15—C14	174.8 (4)
C2—C3—C4—O1	11.4 (8)	C13—C14—C15—O2	−33.8 (7)
C2—C3—C4—N1	−170.7 (5)	C13—C14—C15—N3	146.7 (5)
C6—N2—C5—N1	176.4 (4)	C17—N4—C16—N3	−175.7 (4)
C6—N2—C5—S1	−2.2 (7)	C17—N4—C16—S2	4.1 (7)
C4—N1—C5—N2	−0.5 (7)	C15—N3—C16—N4	−6.3 (7)
C4—N1—C5—S1	178.3 (4)	C15—N3—C16—S2	173.9 (4)
C5—N2—C6—C7	−71.4 (6)	C16—N4—C17—C18	−85.2 (6)
C5—N2—C6—C11	111.9 (5)	C16—N4—C17—C22	96.6 (6)
C11—C6—C7—C8	−1.3 (8)	C22—C17—C18—C19	−1.0 (9)
N2—C6—C7—C8	−178.0 (5)	N4—C17—C18—C19	−179.0 (5)
C6—C7—C8—C9	0.1 (9)	C17—C18—C19—C20	0.9 (11)
C7—C8—C9—C10	0.9 (10)	C18—C19—C20—C21	−0.7 (12)
C8—C9—C10—C11	−0.8 (10)	C19—C20—C21—C22	0.5 (12)
C7—C6—C11—C10	1.4 (8)	C18—C17—C22—C21	0.8 (9)
N2—C6—C11—C10	178.1 (5)	N4—C17—C22—C21	178.9 (5)
C9—C10—C11—C6	−0.3 (9)	C20—C21—C22—C17	−0.6 (11)

Cg1 and Cg2 are the centroids of the C6–C11 and C17–C22 rings, respectively.

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	2.02	2.690 (6)	134
N4—H4···O2	0.86	2.03	2.687 (6)	133
C3—H3A···Br1	0.97	2.84	3.321 (6)	112
C14—H14B···Br2	0.97	2.86	3.293 (5)	108
N2—H2···O2	0.86	2.41	3.140 (5)	143
N4—H4···O1	0.86	2.33	3.049 (6)	142
N1—H1···S2i	0.86	2.53	3.386 (4)	173
C14—H14A···S2ii	0.97	2.78	3.711 (6)	160
N3—H3···S1iii	0.86	2.59	3.445 (4)	176
C2—H2A···Cg2	0.97	2.69	3.405 (8)	131
C13—H13A···Cg1	0.97	2.83	3.708 (6)	150

Table 1

Hydrogen-bond geometry (Å, °)

Cg1 and Cg2 are the centroids of the C6–C11 and C17–C22 rings, respectively.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1	0.86	2.02	2.690 (6)	134
N4—H4⋯O2	0.86	2.03	2.687 (6)	133
N2—H2⋯O2	0.86	2.41	3.140 (5)	143
N4—H4⋯O1	0.86	2.33	3.049 (6)	142
N1—H1⋯S2i	0.86	2.53	3.386 (4)	173
C14—H14A⋯S2ii	0.97	2.78	3.711 (6)	160
N3—H3⋯S1iii	0.86	2.59	3.445 (4)	176
C2—H2A⋯Cg2	0.97	2.69	3.405 (8)	131
C13—H13A⋯Cg1	0.97	2.83	3.708 (6)	150

Symmetry codes: (i) ; (ii) ; (iii) .