1-(4-Chloro-butano-yl)-3-(3-chloro-phen-yl)thio-urea.

The two independent mol-ecules in the asymmetric unit of the title compound, C11H12Cl2N2OS, exhibit different conformations, with the benzene ring and the N2CS thio-urea group forming dihedral angles of 87.40 (18) and 69.42 (15)°. An intra-molecular N-H⋯O hydrogen bond is present in each mol-ecule. Two further N-H⋯O hydrogen bonds link the independent mol-ecules into a dimer. In the crystal, the dimers are linked by N-H⋯S and C-H⋯S hydrogen bonds, forming chains parallel to the c axis.

Related literature

For applications and biological activities of thio­urea derivatives, see: Abbas et al. (2013 ▶). For the crystal structure of a related compound, see: Yusof et al. (2012 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C11H12Cl2N2OS

M = 291.19

Monoclinic,

a = 14.7762 (8) Å

b = 10.9400 (6) Å

c = 17.8153 (10) Å

β = 111.327 (2)°

V = 2682.7 (3) Å3

Z = 8

Mo Kα radiation

μ = 0.62 mm−1

T = 296 K

0.41 × 0.35 × 0.30 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T min = 0.784, T max = 0.835

49874 measured reflections

4987 independent reflections

3897 reflections with I > 2σ(I)

R int = 0.046

Refinement

R[F 2 > 2σ(F 2)] = 0.058

wR(F 2) = 0.162

S = 1.05

4987 reflections

323 parameters

4 restraints

H atoms treated by a mixture of independent and constrained refinement

Δρmax = 1.51 e Å−3

Δρmin = −0.83 e Å−3

Data collection: SMART (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); 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 and PLATON (Spek, 2009 ▶).

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536814009295/rz5121sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536814009295/rz5121Isup2.hkl

Click here for additional data file.

Supporting information file. DOI: 10.1107/S1600536814009295/rz5121Isup3.cml

CCDC reference: 999317

Additional supporting information: crystallographic information; 3D view; checkCIF report

C11H12Cl2N2OS	F(000) = 1200
Mr = 291.19	Dx = 1.442 Mg m−3
Monoclinic, P21/c	Mo Kα radiation, λ = 0.71073 Å
Hall symbol: -P 2ybc	Cell parameters from 9934 reflections
a = 14.7762 (8) Å	θ = 2.9–25.5°
b = 10.9400 (6) Å	µ = 0.62 mm−1
c = 17.8153 (10) Å	T = 296 K
β = 111.327 (2)°	Block, colourless
V = 2682.7 (3) Å3	0.41 × 0.35 × 0.30 mm
Z = 8

Bruker SMART APEX CCD area-detector diffractometer	4987 independent reflections
Radiation source: fine-focus sealed tube	3897 reflections with I > 2σ(I)
Graphite monochromator	Rint = 0.046
Detector resolution: 83.66 pixels mm-1	θmax = 25.5°, θmin = 2.9°
ω scan	h = −17→17
Absorption correction: multi-scan (SADABS; Bruker, 2009)	k = −13→13
Tmin = 0.784, Tmax = 0.835	l = −21→21
49874 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) = 0.162	H atoms treated by a mixture of independent and constrained refinement
S = 1.05	w = 1/[σ2(Fo2) + (0.0699P)2 + 5.078P] where P = (Fo2 + 2Fc2)/3
4987 reflections	(Δ/σ)max = 0.001
323 parameters	Δρmax = 1.51 e Å−3
4 restraints	Δρmin = −0.83 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
Cl1	1.20900 (11)	0.68433 (14)	0.71321 (7)	0.0842 (4)
Cl2	0.53415 (11)	1.04818 (15)	0.11355 (8)	0.0871 (4)
Cl3	0.47334 (9)	0.68932 (12)	0.00986 (9)	0.0842 (4)
Cl4	1.26802 (10)	0.33013 (12)	0.45687 (9)	0.0839 (4)
S1	0.75626 (6)	1.01805 (8)	0.46585 (5)	0.0406 (2)
S2	1.01747 (6)	0.48468 (9)	0.16368 (5)	0.0397 (2)
O1	0.92224 (18)	0.6927 (2)	0.42275 (15)	0.0509 (7)
O2	0.79236 (17)	0.6402 (3)	0.25577 (15)	0.0571 (8)
N1	0.90164 (18)	0.8658 (3)	0.48549 (16)	0.0327 (6)
N2	0.7673 (2)	0.8405 (3)	0.36889 (17)	0.0400 (7)
N3	0.84653 (19)	0.5491 (3)	0.16566 (16)	0.0355 (6)
N4	0.97653 (19)	0.5835 (3)	0.28377 (17)	0.0405 (7)
C1	1.1947 (3)	0.6227 (4)	0.6168 (2)	0.0580 (11)
H1A	1.2353	0.6683	0.5944	0.070*
H1B	1.2167	0.5385	0.6233	0.070*
C2	1.0906 (3)	0.6275 (3)	0.5587 (2)	0.0433 (8)
H2A	1.0863	0.5891	0.5084	0.052*
H2B	1.0502	0.5812	0.5809	0.052*
C3	1.0526 (2)	0.7563 (3)	0.5420 (2)	0.0429 (8)
H3A	1.0506	0.7913	0.5914	0.051*
H3B	1.0974	0.8046	0.5258	0.051*
C4	0.9534 (2)	0.7651 (3)	0.4779 (2)	0.0362 (7)
C5	0.8088 (2)	0.9018 (3)	0.43661 (18)	0.0325 (7)
C6	0.6695 (3)	0.8650 (4)	0.3146 (2)	0.0428 (9)
C7	0.6542 (3)	0.9400 (4)	0.2506 (2)	0.0484 (9)
H7	0.7055	0.9786	0.2417	0.058*
C8	0.5567 (3)	0.9572 (4)	0.1977 (2)	0.0543 (10)
C9	0.4823 (3)	0.9004 (5)	0.2106 (3)	0.0635 (12)
H9	0.4190	0.9126	0.1749	0.076*
C10	0.4990 (3)	0.8265 (5)	0.2745 (3)	0.0674 (13)
H10	0.4475	0.7882	0.2832	0.081*
C11	0.5940 (3)	0.8079 (4)	0.3275 (2)	0.0567 (11)
H11	0.6062	0.7566	0.3717	0.068*
C12	0.4953 (3)	0.6064 (5)	0.1009 (3)	0.0606 (11)
H12A	0.4501	0.6334	0.1256	0.073*
H12B	0.4838	0.5201	0.0885	0.073*
C13	0.5976 (2)	0.6237 (4)	0.1596 (2)	0.0523 (10)
H13A	0.6107	0.7106	0.1674	0.063*
H13B	0.6027	0.5891	0.2111	0.063*
C14	0.6733 (2)	0.5662 (3)	0.1331 (2)	0.0383 (8)
H14A	0.6624	0.4787	0.1278	0.046*
H14B	0.6668	0.5981	0.0806	0.046*
C15	0.7744 (2)	0.5901 (3)	0.1911 (2)	0.0376 (8)
C16	0.9453 (2)	0.5431 (3)	0.20854 (18)	0.0310 (7)
C17	1.0758 (2)	0.5800 (3)	0.33715 (18)	0.0330 (7)
C18	1.1187 (2)	0.4690 (3)	0.3653 (2)	0.0385 (8)
H18	1.0850	0.3961	0.3481	0.046*
C19	1.2132 (3)	0.4690 (3)	0.4198 (2)	0.0414 (8)
C20	1.2647 (2)	0.5753 (4)	0.4454 (2)	0.0473 (9)
H20	1.3286	0.5732	0.4816	0.057*
C21	1.2201 (3)	0.6843 (4)	0.4166 (3)	0.0521 (10)
H21	1.2539	0.7571	0.4336	0.062*
C22	1.1247 (3)	0.6873 (3)	0.3621 (2)	0.0426 (8)
H22	1.0945	0.7615	0.3429	0.051*
H1	0.923 (2)	0.912 (3)	0.5285 (13)	0.033 (9)*
H3	0.826 (2)	0.521 (3)	0.1164 (9)	0.030 (9)*
H4	0.933 (2)	0.609 (3)	0.303 (2)	0.043 (10)*
H2	0.801 (3)	0.779 (3)	0.360 (2)	0.053 (12)*

	U11	U22	U33	U12	U13	U23
Cl1	0.0966 (10)	0.0931 (9)	0.0404 (6)	0.0185 (8)	−0.0019 (6)	−0.0008 (6)
Cl2	0.0826 (9)	0.1067 (11)	0.0642 (7)	0.0309 (8)	0.0174 (7)	0.0311 (7)
Cl3	0.0508 (6)	0.0749 (8)	0.0930 (9)	0.0089 (6)	−0.0142 (6)	0.0095 (7)
Cl4	0.0744 (8)	0.0630 (7)	0.0882 (9)	0.0298 (6)	−0.0016 (7)	0.0157 (6)
S1	0.0343 (4)	0.0466 (5)	0.0349 (4)	0.0111 (4)	0.0057 (3)	−0.0043 (4)
S2	0.0316 (4)	0.0535 (5)	0.0337 (4)	0.0046 (4)	0.0116 (3)	−0.0006 (4)
O1	0.0388 (14)	0.0542 (16)	0.0470 (15)	0.0099 (12)	0.0005 (12)	−0.0182 (13)
O2	0.0313 (13)	0.087 (2)	0.0415 (14)	0.0122 (13)	−0.0002 (11)	−0.0240 (14)
N1	0.0259 (13)	0.0376 (15)	0.0301 (14)	0.0035 (11)	0.0048 (11)	−0.0062 (12)
N2	0.0285 (14)	0.0493 (18)	0.0343 (15)	0.0103 (13)	0.0018 (12)	−0.0088 (13)
N3	0.0247 (13)	0.0504 (17)	0.0265 (14)	0.0015 (12)	0.0036 (11)	−0.0055 (12)
N4	0.0257 (14)	0.0582 (19)	0.0324 (15)	0.0087 (13)	0.0042 (12)	−0.0090 (13)
C1	0.048 (2)	0.070 (3)	0.046 (2)	0.022 (2)	0.0051 (18)	0.001 (2)
C2	0.0375 (19)	0.047 (2)	0.0403 (19)	0.0074 (16)	0.0084 (15)	−0.0009 (16)
C3	0.0273 (16)	0.045 (2)	0.047 (2)	0.0056 (15)	0.0021 (15)	−0.0064 (16)
C4	0.0287 (16)	0.0417 (19)	0.0355 (17)	0.0030 (14)	0.0086 (14)	−0.0005 (15)
C5	0.0275 (15)	0.0380 (17)	0.0305 (16)	0.0012 (13)	0.0087 (13)	0.0049 (14)
C6	0.0376 (19)	0.051 (2)	0.0306 (17)	0.0129 (16)	0.0015 (14)	−0.0097 (16)
C7	0.046 (2)	0.055 (2)	0.039 (2)	0.0085 (18)	0.0091 (16)	−0.0054 (17)
C8	0.056 (2)	0.059 (2)	0.040 (2)	0.016 (2)	0.0090 (18)	0.0009 (18)
C9	0.037 (2)	0.084 (3)	0.059 (3)	0.010 (2)	0.0051 (19)	−0.007 (2)
C10	0.034 (2)	0.097 (4)	0.062 (3)	−0.001 (2)	0.007 (2)	−0.005 (3)
C11	0.038 (2)	0.077 (3)	0.047 (2)	0.001 (2)	0.0051 (17)	−0.003 (2)
C12	0.0295 (19)	0.080 (3)	0.068 (3)	−0.0057 (19)	0.0134 (19)	−0.016 (2)
C13	0.0291 (18)	0.075 (3)	0.051 (2)	−0.0026 (18)	0.0115 (16)	−0.015 (2)
C14	0.0277 (16)	0.046 (2)	0.0366 (18)	0.0010 (14)	0.0056 (14)	−0.0046 (15)
C15	0.0281 (16)	0.0451 (19)	0.0349 (18)	0.0054 (14)	0.0058 (14)	−0.0021 (15)
C16	0.0264 (15)	0.0327 (16)	0.0300 (16)	0.0016 (12)	0.0055 (13)	0.0039 (13)
C17	0.0257 (15)	0.0437 (19)	0.0269 (15)	0.0046 (14)	0.0065 (13)	−0.0032 (14)
C18	0.0343 (17)	0.0391 (18)	0.0373 (18)	−0.0011 (14)	0.0073 (14)	−0.0051 (15)
C19	0.0353 (18)	0.048 (2)	0.0374 (18)	0.0128 (16)	0.0088 (15)	0.0022 (16)
C20	0.0242 (16)	0.069 (3)	0.042 (2)	0.0025 (17)	0.0035 (14)	−0.0063 (18)
C21	0.037 (2)	0.050 (2)	0.061 (2)	−0.0093 (17)	0.0092 (18)	−0.0112 (19)
C22	0.0369 (18)	0.0385 (19)	0.047 (2)	0.0044 (15)	0.0084 (16)	0.0034 (16)

Cl1—C1	1.784 (4)	C6—C7	1.357 (5)
Cl2—C8	1.728 (4)	C6—C11	1.369 (6)
Cl3—C12	1.782 (5)	C7—C8	1.418 (5)
Cl4—C19	1.736 (4)	C7—H7	0.9300
S1—C5	1.669 (3)	C8—C9	1.354 (6)
S2—C16	1.674 (3)	C9—C10	1.343 (7)
O1—C4	1.215 (4)	C9—H9	0.9300
O2—C15	1.215 (4)	C10—C11	1.393 (6)
N1—C4	1.376 (4)	C10—H10	0.9300
N1—C5	1.388 (4)	C11—H11	0.9300
N1—H1	0.876 (10)	C12—C13	1.504 (5)
N2—C5	1.321 (4)	C12—H12A	0.9700
N2—C6	1.441 (4)	C12—H12B	0.9700
N2—H2	0.876 (10)	C13—C14	1.502 (5)
N3—C15	1.376 (4)	C13—H13A	0.9700
N3—C16	1.381 (4)	C13—H13B	0.9700
N3—H3	0.872 (10)	C14—C15	1.497 (4)
N4—C16	1.325 (4)	C14—H14A	0.9700
N4—C17	1.429 (4)	C14—H14B	0.9700
N4—H4	0.874 (10)	C17—C22	1.365 (5)
C1—C2	1.511 (5)	C17—C18	1.378 (5)
C1—H1A	0.9700	C18—C19	1.381 (5)
C1—H1B	0.9700	C18—H18	0.9300
C2—C3	1.506 (5)	C19—C20	1.373 (5)
C2—H2A	0.9700	C20—C21	1.369 (6)
C2—H2B	0.9700	C20—H20	0.9300
C3—C4	1.499 (4)	C21—C22	1.391 (5)
C3—H3A	0.9700	C21—H21	0.9300
C3—H3B	0.9700	C22—H22	0.9300
C4—N1—C5	128.6 (3)	C9—C10—C11	119.5 (4)
C4—N1—H1	121 (2)	C9—C10—H10	120.3
C5—N1—H1	110 (2)	C11—C10—H10	120.3
C5—N2—C6	122.5 (3)	C6—C11—C10	120.1 (4)
C5—N2—H2	116 (3)	C6—C11—H11	120.0
C6—N2—H2	121 (3)	C10—C11—H11	120.0
C15—N3—C16	128.5 (3)	C13—C12—Cl3	111.9 (3)
C15—N3—H3	115 (2)	C13—C12—H12A	109.2
C16—N3—H3	117 (2)	Cl3—C12—H12A	109.2
C16—N4—C17	124.0 (3)	C13—C12—H12B	109.2
C16—N4—H4	118 (2)	Cl3—C12—H12B	109.2
C17—N4—H4	118 (2)	H12A—C12—H12B	107.9
C2—C1—Cl1	112.4 (3)	C14—C13—C12	113.8 (3)
C2—C1—H1A	109.1	C14—C13—H13A	108.8
Cl1—C1—H1A	109.1	C12—C13—H13A	108.8
C2—C1—H1B	109.1	C14—C13—H13B	108.8
Cl1—C1—H1B	109.1	C12—C13—H13B	108.8
H1A—C1—H1B	107.9	H13A—C13—H13B	107.7
C3—C2—C1	112.4 (3)	C15—C14—C13	112.4 (3)
C3—C2—H2A	109.1	C15—C14—H14A	109.1
C1—C2—H2A	109.1	C13—C14—H14A	109.1
C3—C2—H2B	109.1	C15—C14—H14B	109.1
C1—C2—H2B	109.1	C13—C14—H14B	109.1
H2A—C2—H2B	107.9	H14A—C14—H14B	107.9
C4—C3—C2	113.7 (3)	O2—C15—N3	122.0 (3)
C4—C3—H3A	108.8	O2—C15—C14	123.5 (3)
C2—C3—H3A	108.8	N3—C15—C14	114.4 (3)
C4—C3—H3B	108.8	N4—C16—N3	116.9 (3)
C2—C3—H3B	108.8	N4—C16—S2	124.2 (2)
H3A—C3—H3B	107.7	N3—C16—S2	118.8 (2)
O1—C4—N1	122.8 (3)	C22—C17—C18	121.4 (3)
O1—C4—C3	123.5 (3)	C22—C17—N4	119.2 (3)
N1—C4—C3	113.7 (3)	C18—C17—N4	119.4 (3)
N2—C5—N1	117.0 (3)	C17—C18—C19	118.0 (3)
N2—C5—S1	123.9 (2)	C17—C18—H18	121.0
N1—C5—S1	119.1 (2)	C19—C18—H18	121.0
C7—C6—C11	121.4 (3)	C20—C19—C18	122.1 (3)
C7—C6—N2	119.8 (4)	C20—C19—Cl4	119.3 (3)
C11—C6—N2	118.8 (3)	C18—C19—Cl4	118.7 (3)
C6—C7—C8	117.2 (4)	C21—C20—C19	118.7 (3)
C6—C7—H7	121.4	C21—C20—H20	120.7
C8—C7—H7	121.4	C19—C20—H20	120.7
C9—C8—C7	121.2 (4)	C20—C21—C22	120.6 (4)
C9—C8—Cl2	120.0 (3)	C20—C21—H21	119.7
C7—C8—Cl2	118.8 (4)	C22—C21—H21	119.7
C10—C9—C8	120.7 (4)	C17—C22—C21	119.3 (3)
C10—C9—H9	119.7	C17—C22—H22	120.3
C8—C9—H9	119.7	C21—C22—H22	120.3
Cl1—C1—C2—C3	61.8 (4)	Cl3—C12—C13—C14	−68.4 (5)
C1—C2—C3—C4	173.7 (3)	C12—C13—C14—C15	177.4 (4)
C5—N1—C4—O1	1.6 (6)	C16—N3—C15—O2	8.2 (6)
C5—N1—C4—C3	179.5 (3)	C16—N3—C15—C14	−171.1 (3)
C2—C3—C4—O1	−28.8 (5)	C13—C14—C15—O2	6.6 (5)
C2—C3—C4—N1	153.3 (3)	C13—C14—C15—N3	−174.1 (3)
C6—N2—C5—N1	177.1 (3)	C17—N4—C16—N3	177.8 (3)
C6—N2—C5—S1	−2.8 (5)	C17—N4—C16—S2	−1.4 (5)
C4—N1—C5—N2	−8.1 (5)	C15—N3—C16—N4	−1.2 (5)
C4—N1—C5—S1	171.8 (3)	C15—N3—C16—S2	178.0 (3)
C5—N2—C6—C7	95.8 (4)	C16—N4—C17—C22	113.8 (4)
C5—N2—C6—C11	−86.6 (5)	C16—N4—C17—C18	−69.3 (5)
C11—C6—C7—C8	0.2 (6)	C22—C17—C18—C19	0.0 (5)
N2—C6—C7—C8	177.8 (3)	N4—C17—C18—C19	−176.9 (3)
C6—C7—C8—C9	−0.3 (6)	C17—C18—C19—C20	−0.8 (5)
C6—C7—C8—Cl2	−178.0 (3)	C17—C18—C19—Cl4	179.3 (3)
C7—C8—C9—C10	0.4 (7)	C18—C19—C20—C21	1.0 (6)
Cl2—C8—C9—C10	178.0 (4)	Cl4—C19—C20—C21	−179.1 (3)
C8—C9—C10—C11	−0.4 (7)	C19—C20—C21—C22	−0.4 (6)
C7—C6—C11—C10	−0.2 (6)	C18—C17—C22—C21	0.5 (5)
N2—C6—C11—C10	−177.8 (4)	N4—C17—C22—C21	177.4 (3)
C9—C10—C11—C6	0.3 (7)	C20—C21—C22—C17	−0.3 (6)

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.89 (4)	1.97 (4)	2.679 (4)	136 (3)
N2—H2···O2	0.89 (4)	2.37 (3)	3.089 (4)	139 (3)
N4—H4···O1	0.88 (3)	2.38 (3)	3.106 (4)	140 (3)
N4—H4···O2	0.88 (3)	1.97 (3)	2.656 (4)	134 (3)
C3—H3A···Cl1	0.97	2.80	3.184 (4)	104
N1—H1···S2i	0.88 (3)	2.57 (2)	3.425 (3)	167 (3)
N3—H3···S1ii	0.87 (2)	2.54 (2)	3.397 (3)	169 (3)
C3—H3B···S1iii	0.97	2.87	3.792 (3)	160

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1	0.89 (4)	1.97 (4)	2.679 (4)	136 (3)
N2—H2⋯O2	0.89 (4)	2.37 (3)	3.089 (4)	139 (3)
N4—H4⋯O1	0.88 (3)	2.38 (3)	3.106 (4)	140 (3)
N4—H4⋯O2	0.88 (3)	1.97 (3)	2.656 (4)	134 (3)
N1—H1⋯S2i	0.88 (3)	2.57 (2)	3.425 (3)	167 (3)
N3—H3⋯S1ii	0.87 (2)	2.54 (2)	3.397 (3)	169 (3)
C3—H3B⋯S1iii	0.97	2.87	3.792 (3)	160

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