N-(4-Chloro­butano­yl)-N′-phenyl­thio­urea

Yamin, B.M.; Othman, N.E.A.; Yusof, M.S.M.; Embong, F.

doi:10.1107/S1600536811001498

organic compounds

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o419

doi:10.1107/S1600536811001498

Open

access

N-(4-Chlorobutanoyl)-N′-phenylthiourea

Bohari M. Yamin,^a ^* Nur Eliyanti Ali Othman,^a M. Sukeri M. Yusof ^b and Farhana. Embong ^b

^aSchool of Chemical Sciences and Food Technology, Universiti Kebangsaan Malaysia, UKM 43600 Bangi Selangor, Malaysia, and ^bDepartment of Chemical Sciences, Faculty of Science and Technology, Universiti Malaysia Terengganu, Menggabang Telipot, 21030 Kuala Terengganu, Malaysia
^*Correspondence e-mail: bohari@ukm.my

(Received 29 December 2010; accepted 11 January 2011; online 15 January 2011)

The asymmetric unit of the title compound, C₁₁H₁₃ClN₂OS, contains two independent molecules. Both molecules maintain a trans–cis configuration with respect to the position of the carbonyl group and the benzene ring against the thione group across the C—N bonds. The molecules are stabilized by intramolecular N—H⋯O hydrogen bonds. In the crystal, the molecules are linked by intermolecular N—H⋯S, N—H⋯O and C—H⋯S hydrogen bonds into chains along the c axis. C—H⋯π interactions further stabilize the crystal structure.

Related literature

For the biological properties of thiourea derivatives, see; Sun et al. (2006 ); Figueiredo et al. (2006 ). For a related structure, see: Othman et al. (2010 ); For standard bond lengths, see: Allen et al. (1987 ).

Experimental

Crystal data

C₁₁H₁₃ClN₂OS
M_r = 256.74
Monoclinic, P 2₁ /c
a = 14.610 (3) Å
b = 10.244 (2) Å
c = 18.230 (4) Å
β = 112.408 (4)°
V = 2522.5 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 298 K
0.50 × 0.49 × 0.09 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2000 ) T_min = 0.807, T_max = 0.961
14531 measured reflections
4706 independent reflections
3195 reflections with I > 2/s(I)
R_int = 0.043

Refinement

R[F² > 2σ(F²)] = 0.048
wR(F²) = 0.131
S = 1.02
4706 reflections
289 parameters
H-atom parameters constrained
Δρ_max = 0.48 e Å⁻³
Δρ_min = −0.29 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

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

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2⋯O1	0.86	2.04	2.701 (3)	134
N4—H4⋯O2	0.86	2.03	2.692 (3)	133
N1—H1⋯S2ⁱ	0.86	2.53	3.382 (2)	173
N2—H2⋯O2ⁱⁱ	0.86	2.40	3.142 (3)	144
N3—H3⋯S1ⁱⁱⁱ	0.86	2.58	3.439 (2)	175
N4—H4⋯O1ⁱⁱ	0.86	2.32	3.057 (3)	143
C14—H14A⋯S2^iv	0.97	2.73	3.676 (3)	166
C2—H2A⋯Cg2ⁱⁱ	0.97	2.80	3.419 (4)	123
C13—H13A⋯Cg1ⁱⁱ	0.97	2.83	3.417 (3)	153
Symmetry codes: (i) $[-x+1, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (ii) -x+1, -y+1, -z+1; (iii) $[-x+1, y+{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x, -y+1, -z.

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 ).

Supporting information

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811001498/hg2783sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536811001498/hg2783Isup2.hkl

checkCIF report

Comment top

The continuing work on the synthesis of thiourea derivatives is driven by their chemical and biological properties (Sun et al. ,2006). Some thiourea derivatives such as N-[1-(4R)-(4-isopropyl-1-methylcyclohexenyl)]-N'-[2 - (butyl)]thiourea is known to possess anticancer activity (Figueiredo et al., 2006). The title compound (I), is analogous to the previously reported N-(3-chloropropionyl)-N'-(phenyl)thiourea (Othman et al., 2010) except the terminal chlorine atom is attached at the γ position, 3 (C—C) bonds away from the carbonyl group. The asymmetric unit consists of two independent molecules (Fig.1). Unlike its 3-chloropropionyl analog, the butanoyl group is not planar. However, the thiourea C4/N1/C5/S1/N2/C6, C15/N3/C16/S2/N4/C17 fragments and the benzene rings, (C6—C11) and (C17—C22) are each planar with maximum deviation of 0.059 (2)Å for N3 atom from the least square plane. In each molecule, the benzene ring is vertical to the thiourea fragment with dihedral angle of 72.98 (12)° and 81.47 (14)°, respectively. The bond lengths and angles are in normal ranges (Allen et al., 1987) and comparable to those in the N-(3-chloropropionyl)-N'-(phenyl)thiourea. Both molecules maintain the trans-cis configuration with respect to the position of the carbonoyl and phenyl groups against the thiono C=S bond across their C—N bonds. Such configuration allows the formation of intramolecular hydrogen bonds between the carbonyl oxygen atom and thioamide hydrogen atom, C4—O1···H2- and C15—O2···H4, in both molecules. In the crystal stucture, the molecules are linked by N1—H1···S2, N2—H2···O2, N3—H3···S1, N4—H4···O1 and C14—H14A···S2 intermolecular hydrogen bonds (symmetry codes as in Table 2) forming infinite one-dimensional chains along the c axis (Fig.2).The molecule is also stablized by C2—H2A···π and C13—H13A···π with the centroid benzene ring Cg2,(C6—C11) and Cg1,(C17—C22) respectively (Table 2).

Related literature top

For the biological properties of thiurea derivatives, see; Sun et al. (2006); Figueiredo et al. (2006). For a related structure, see: Othman et al. (2010); For standard bond lengths, see: Allen et al. (1987).

Experimental top

30 ml acetone solution of aniline (1.33 g, 14 mmol) was added into 30 ml acetone containing 4-chlorobutanoy chloride (2.00 g, 14 mmol) and ammonium thiocyanate (1.09 g, 14 mmol). The mixture was refluxed for 2 h. The solution was filtered and left to evaporate at room temperature. The yellowish precipitate obtained after a few days, was washed with water and cold ethanol. The colourless crytals were obtained by recrystallization from ethanol. Yield 90%; m.p 392.3–393.2 K.

Computing details top

Data collection: SMART (Bruker, 2000); cell refinement: SAINT (Bruker, 2000); data reduction: SAINT (Bruker, 2000); 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).

Figures top

	Fig. 1. The molecular structure of (I), with displacement ellipsods are drawn at the 50% probability level. the dashed line denote the intramolecular hydrogen bonds.
	Fig. 2. The molecular packing of (I) viewed down the b-axis. The dashed line denote the intermolecular hydrogen bonds.

N-(4-Chlorobutanoyl)-N'-phenylthiourea top

Crystal data top

C₁₁H₁₃ClN₂OS	F(000) = 1072
M_r = 256.74	D_x = 1.352 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 = 14.610 (3) Å	Cell parameters from 3372 reflections
b = 10.244 (2) Å	θ = 2.3–25.5°
c = 18.230 (4) Å	µ = 0.45 mm⁻¹
β = 112.408 (4)°	T = 298 K
V = 2522.5 (9) Å³	Slab, colourless
Z = 8	0.50 × 0.49 × 0.09 mm

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4706 independent reflections
Radiation source: fine-focus sealed tube	3195 reflections with I > 2/s(I)
Graphite monochromator	R_int = 0.043
Detector resolution: 83.66 pixels mm^-1	θ_max = 25.5°, θ_min = 2.3°
ω scans	h = −17→16
Absorption correction: multi-scan (SADABS; Bruker, 2000)	k = −12→11
T_min = 0.807, T_max = 0.961	l = −22→20
14531 measured reflections

Refinement top

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)] = 0.048	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.131	H-atom parameters constrained
S = 1.02	w = 1/[σ²(F_o²) + (0.0595P)² + 0.9697P] where P = (F_o² + 2F_c²)/3
4706 reflections	(Δ/σ)_max < 0.001
289 parameters	Δρ_max = 0.48 e Å⁻³
0 restraints	Δρ_min = −0.29 e Å⁻³

Crystal data top

C₁₁H₁₃ClN₂OS	V = 2522.5 (9) Å³
M_r = 256.74	Z = 8
Monoclinic, P2₁/c	Mo Kα radiation
a = 14.610 (3) Å	µ = 0.45 mm⁻¹
b = 10.244 (2) Å	T = 298 K
c = 18.230 (4) Å	0.50 × 0.49 × 0.09 mm
β = 112.408 (4)°

Data collection top

Bruker SMART APEX CCD area-detector diffractometer	4706 independent reflections
Absorption correction: multi-scan (SADABS; Bruker, 2000)	3195 reflections with I > 2/s(I)
T_min = 0.807, T_max = 0.961	R_int = 0.043
14531 measured reflections

Refinement top

R[F² > 2σ(F²)] = 0.048	0 restraints
wR(F²) = 0.131	H-atom parameters constrained
S = 1.02	Δρ_max = 0.48 e Å⁻³
4706 reflections	Δρ_min = −0.29 e Å⁻³
289 parameters

Special details top

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.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
Cl1	0.49537 (8)	0.21955 (15)	0.48980 (7)	0.1177 (5)
Cl2	−0.21432 (6)	0.81829 (9)	−0.21567 (5)	0.0734 (3)
S1	1.01893 (5)	−0.02943 (8)	0.66961 (4)	0.0505 (2)
S2	0.24956 (5)	0.47421 (8)	0.02400 (4)	0.0479 (2)
O1	0.79636 (14)	0.1555 (2)	0.75863 (12)	0.0602 (6)
O2	0.07429 (14)	0.80422 (18)	0.07521 (11)	0.0540 (5)
N1	0.84965 (15)	0.0558 (2)	0.67035 (12)	0.0433 (5)
H1	0.8298	0.0332	0.6213	0.052*
N2	0.98310 (15)	0.0728 (2)	0.79027 (12)	0.0444 (6)
H2	0.9429	0.1100	0.8080	0.053*
N3	0.09962 (14)	0.6311 (2)	0.00710 (12)	0.0411 (5)
H3	0.0729	0.5877	−0.0363	0.049*
N4	0.23236 (15)	0.6444 (2)	0.12761 (13)	0.0457 (6)
H4	0.2007	0.7065	0.1393	0.055*
C1	0.4980 (2)	0.1639 (4)	0.5816 (2)	0.0839 (12)
H1A	0.4521	0.2154	0.5966	0.101*
H1B	0.4756	0.0739	0.5760	0.101*
C2	0.5993 (2)	0.1718 (4)	0.6469 (2)	0.0709 (10)
H2A	0.6214	0.2619	0.6528	0.085*
H2B	0.5946	0.1452	0.6965	0.085*
C3	0.67435 (19)	0.0891 (3)	0.63244 (17)	0.0539 (8)
H3A	0.6747	0.1104	0.5807	0.065*
H3B	0.6551	−0.0017	0.6313	0.065*
C4	0.77790 (19)	0.1056 (3)	0.69406 (16)	0.0449 (7)
C5	0.94940 (18)	0.0371 (2)	0.71449 (15)	0.0394 (6)
C6	1.08327 (18)	0.0522 (3)	0.84386 (15)	0.0415 (6)
C7	1.1446 (2)	0.1570 (3)	0.87086 (18)	0.0564 (8)
H7	1.1220	0.2408	0.8538	0.068*
C8	1.2406 (2)	0.1375 (4)	0.9236 (2)	0.0721 (10)
H8	1.2827	0.2087	0.9423	0.087*
C9	1.2743 (2)	0.0148 (4)	0.9486 (2)	0.0752 (11)
H9	1.3394	0.0026	0.9836	0.090*
C10	1.2127 (2)	−0.0904 (4)	0.9225 (2)	0.0722 (10)
H10	1.2355	−0.1738	0.9404	0.087*
C11	1.1162 (2)	−0.0724 (3)	0.86907 (18)	0.0570 (8)
H11	1.0741	−0.1436	0.8505	0.068*
C12	−0.2044 (2)	0.8804 (3)	−0.12092 (18)	0.0609 (8)
H12A	−0.2282	0.9697	−0.1271	0.073*
H12B	−0.2462	0.8291	−0.1015	0.073*
C13	−0.09988 (19)	0.8768 (3)	−0.06106 (17)	0.0489 (7)
H13A	−0.0978	0.9152	−0.0118	0.059*
H13B	−0.0583	0.9291	−0.0803	0.059*
C14	−0.05878 (19)	0.7394 (3)	−0.04492 (18)	0.0488 (7)
H14A	−0.1029	0.6861	−0.0290	0.059*
H14B	−0.0576	0.7031	−0.0937	0.059*
C15	0.04357 (19)	0.7319 (3)	0.01824 (16)	0.0418 (6)
C16	0.19336 (17)	0.5905 (3)	0.05662 (15)	0.0382 (6)
C17	0.32572 (19)	0.6032 (3)	0.18617 (16)	0.0446 (7)
C18	0.4123 (2)	0.6520 (3)	0.18414 (19)	0.0616 (8)
H18	0.4111	0.7105	0.1448	0.074*
C19	0.5016 (2)	0.6125 (4)	0.2418 (2)	0.0790 (11)
H19	0.5608	0.6449	0.2413	0.095*
C20	0.5028 (3)	0.5265 (4)	0.2990 (2)	0.0837 (12)
H20	0.5629	0.5004	0.3375	0.100*
C21	0.4155 (3)	0.4778 (4)	0.3003 (2)	0.0798 (11)
H21	0.4168	0.4189	0.3395	0.096*
C22	0.3259 (2)	0.5167 (3)	0.2432 (2)	0.0610 (8)
H22	0.2666	0.4843	0.2437	0.073*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
Cl1	0.0732 (7)	0.1601 (12)	0.0867 (8)	0.0387 (7)	−0.0065 (6)	0.0182 (8)
Cl2	0.0749 (6)	0.0718 (6)	0.0519 (5)	−0.0005 (4)	−0.0002 (4)	0.0018 (4)
S1	0.0404 (4)	0.0708 (5)	0.0381 (4)	0.0070 (3)	0.0125 (3)	−0.0009 (3)
S2	0.0404 (4)	0.0594 (5)	0.0391 (4)	0.0100 (3)	0.0101 (3)	−0.0034 (3)
O1	0.0449 (11)	0.0779 (14)	0.0470 (13)	0.0125 (10)	0.0053 (9)	−0.0161 (11)
O2	0.0520 (12)	0.0504 (12)	0.0459 (12)	0.0108 (9)	0.0031 (9)	−0.0066 (10)
N1	0.0356 (12)	0.0581 (14)	0.0299 (11)	0.0061 (10)	0.0054 (9)	−0.0013 (10)
N2	0.0354 (12)	0.0555 (14)	0.0364 (13)	0.0069 (10)	0.0071 (10)	−0.0072 (11)
N3	0.0345 (11)	0.0463 (13)	0.0336 (12)	0.0036 (10)	0.0031 (9)	−0.0036 (10)
N4	0.0383 (12)	0.0511 (13)	0.0381 (13)	0.0097 (10)	0.0039 (10)	−0.0053 (11)
C1	0.0357 (17)	0.118 (3)	0.091 (3)	−0.0003 (19)	0.0159 (17)	−0.035 (2)
C2	0.0382 (16)	0.105 (3)	0.062 (2)	0.0053 (17)	0.0103 (15)	−0.021 (2)
C3	0.0397 (15)	0.068 (2)	0.0451 (17)	0.0045 (14)	0.0066 (13)	−0.0058 (15)
C4	0.0390 (14)	0.0520 (17)	0.0382 (16)	0.0057 (13)	0.0084 (12)	−0.0012 (13)
C5	0.0374 (14)	0.0400 (14)	0.0369 (15)	−0.0003 (11)	0.0098 (11)	0.0044 (12)
C6	0.0345 (14)	0.0529 (17)	0.0332 (14)	0.0032 (12)	0.0086 (11)	−0.0041 (12)
C7	0.0450 (16)	0.0573 (19)	0.060 (2)	−0.0001 (14)	0.0126 (15)	−0.0051 (15)
C8	0.0425 (18)	0.088 (3)	0.073 (2)	−0.0110 (18)	0.0077 (16)	−0.019 (2)
C9	0.0387 (17)	0.114 (3)	0.055 (2)	0.016 (2)	−0.0019 (15)	−0.011 (2)
C10	0.063 (2)	0.079 (2)	0.059 (2)	0.028 (2)	0.0061 (17)	0.0068 (19)
C11	0.0519 (18)	0.0562 (18)	0.0532 (19)	0.0038 (15)	0.0093 (14)	−0.0026 (15)
C12	0.0498 (17)	0.068 (2)	0.056 (2)	0.0158 (15)	0.0109 (15)	0.0062 (16)
C13	0.0448 (15)	0.0491 (17)	0.0470 (17)	0.0048 (13)	0.0110 (13)	−0.0001 (13)
C14	0.0381 (15)	0.0448 (16)	0.0534 (18)	0.0024 (12)	0.0061 (13)	0.0022 (13)
C15	0.0399 (14)	0.0410 (15)	0.0404 (16)	0.0015 (12)	0.0106 (12)	0.0044 (13)
C16	0.0349 (13)	0.0425 (15)	0.0356 (14)	−0.0009 (11)	0.0116 (11)	0.0033 (12)
C17	0.0398 (15)	0.0471 (16)	0.0371 (15)	0.0030 (12)	0.0038 (12)	−0.0082 (13)
C18	0.0460 (17)	0.078 (2)	0.0545 (19)	−0.0024 (16)	0.0128 (15)	−0.0066 (17)
C19	0.0416 (18)	0.112 (3)	0.073 (3)	−0.0035 (19)	0.0094 (17)	−0.021 (2)
C20	0.054 (2)	0.094 (3)	0.073 (3)	0.025 (2)	−0.0097 (19)	−0.011 (2)
C21	0.081 (3)	0.067 (2)	0.064 (2)	0.017 (2)	−0.002 (2)	0.0118 (18)
C22	0.0537 (18)	0.0553 (19)	0.061 (2)	0.0008 (15)	0.0074 (16)	0.0025 (16)

Geometric parameters (Å, º) top

Cl1—C1	1.755 (4)	C7—C8	1.379 (4)
Cl2—C12	1.794 (3)	C7—H7	0.9300
S1—C5	1.673 (3)	C8—C9	1.363 (5)
S2—C16	1.679 (3)	C8—H8	0.9300
O1—C4	1.216 (3)	C9—C10	1.368 (5)
O2—C15	1.214 (3)	C9—H9	0.9300
N1—C4	1.375 (3)	C10—C11	1.387 (4)
N1—C5	1.383 (3)	C10—H10	0.9300
N1—H1	0.8600	C11—H11	0.9300
N2—C5	1.329 (3)	C12—C13	1.501 (4)
N2—C6	1.432 (3)	C12—H12A	0.9700
N2—H2	0.8600	C12—H12B	0.9700
N3—C15	1.381 (3)	C13—C14	1.514 (4)
N3—C16	1.386 (3)	C13—H13A	0.9700
N3—H3	0.8600	C13—H13B	0.9700
N4—C16	1.320 (3)	C14—C15	1.502 (4)
N4—C17	1.438 (3)	C14—H14A	0.9700
N4—H4	0.8600	C14—H14B	0.9700
C1—C2	1.507 (4)	C17—C22	1.366 (4)
C1—H1A	0.9700	C17—C18	1.374 (4)
C1—H1B	0.9700	C18—C19	1.387 (5)
C2—C3	1.487 (4)	C18—H18	0.9300
C2—H2A	0.9700	C19—C20	1.360 (6)
C2—H2B	0.9700	C19—H19	0.9300
C3—C4	1.511 (4)	C20—C21	1.378 (6)
C3—H3A	0.9700	C20—H20	0.9300
C3—H3B	0.9700	C21—C22	1.385 (4)
C6—C7	1.365 (4)	C21—H21	0.9300
C6—C11	1.380 (4)	C22—H22	0.9300

C4—N1—C5	129.0 (2)	C9—C10—C11	119.8 (3)
C4—N1—H1	115.5	C9—C10—H10	120.1
C5—N1—H1	115.5	C11—C10—H10	120.1
C5—N2—C6	123.1 (2)	C6—C11—C10	119.3 (3)
C5—N2—H2	118.5	C6—C11—H11	120.4
C6—N2—H2	118.5	C10—C11—H11	120.4
C15—N3—C16	128.5 (2)	C13—C12—Cl2	112.2 (2)
C15—N3—H3	115.7	C13—C12—H12A	109.2
C16—N3—H3	115.7	Cl2—C12—H12A	109.2
C16—N4—C17	122.5 (2)	C13—C12—H12B	109.2
C16—N4—H4	118.7	Cl2—C12—H12B	109.2
C17—N4—H4	118.7	H12A—C12—H12B	107.9
C2—C1—Cl1	113.2 (3)	C12—C13—C14	112.5 (2)
C2—C1—H1A	108.9	C12—C13—H13A	109.1
Cl1—C1—H1A	108.9	C14—C13—H13A	109.1
C2—C1—H1B	108.9	C12—C13—H13B	109.1
Cl1—C1—H1B	108.9	C14—C13—H13B	109.1
H1A—C1—H1B	107.8	H13A—C13—H13B	107.8
C3—C2—C1	113.4 (3)	C15—C14—C13	113.7 (2)
C3—C2—H2A	108.9	C15—C14—H14A	108.8
C1—C2—H2A	108.9	C13—C14—H14A	108.8
C3—C2—H2B	108.9	C15—C14—H14B	108.8
C1—C2—H2B	108.9	C13—C14—H14B	108.8
H2A—C2—H2B	107.7	H14A—C14—H14B	107.7
C2—C3—C4	113.7 (2)	O2—C15—N3	122.4 (2)
C2—C3—H3A	108.8	O2—C15—C14	124.1 (2)
C4—C3—H3A	108.8	N3—C15—C14	113.5 (2)
C2—C3—H3B	108.8	N4—C16—N3	117.6 (2)
C4—C3—H3B	108.8	N4—C16—S2	123.88 (19)
H3A—C3—H3B	107.7	N3—C16—S2	118.51 (19)
O1—C4—N1	123.1 (2)	C22—C17—C18	121.5 (3)
O1—C4—C3	123.8 (2)	C22—C17—N4	118.8 (3)
N1—C4—C3	113.1 (2)	C18—C17—N4	119.7 (3)
N2—C5—N1	117.2 (2)	C17—C18—C19	118.9 (3)
N2—C5—S1	124.53 (19)	C17—C18—H18	120.6
N1—C5—S1	118.25 (19)	C19—C18—H18	120.6
C7—C6—C11	120.7 (3)	C20—C19—C18	120.3 (3)
C7—C6—N2	119.3 (2)	C20—C19—H19	119.9
C11—C6—N2	120.0 (2)	C18—C19—H19	119.9
C6—C7—C8	119.4 (3)	C19—C20—C21	120.4 (3)
C6—C7—H7	120.3	C19—C20—H20	119.8
C8—C7—H7	120.3	C21—C20—H20	119.8
C9—C8—C7	120.5 (3)	C20—C21—C22	120.0 (4)
C9—C8—H8	119.7	C20—C21—H21	120.0
C7—C8—H8	119.7	C22—C21—H21	120.0
C8—C9—C10	120.3 (3)	C17—C22—C21	119.0 (3)
C8—C9—H9	119.9	C17—C22—H22	120.5
C10—C9—H9	119.9	C21—C22—H22	120.5

Cl1—C1—C2—C3	−62.3 (4)	Cl2—C12—C13—C14	−61.6 (3)
C1—C2—C3—C4	175.0 (3)	C12—C13—C14—C15	−176.6 (3)
C5—N1—C4—O1	8.8 (5)	C16—N3—C15—O2	3.3 (4)
C5—N1—C4—C3	−170.0 (3)	C16—N3—C15—C14	−174.7 (2)
C2—C3—C4—O1	16.7 (5)	C13—C14—C15—O2	33.0 (4)
C2—C3—C4—N1	−164.5 (3)	C13—C14—C15—N3	−149.0 (2)
C6—N2—C5—N1	176.3 (2)	C17—N4—C16—N3	175.2 (2)
C6—N2—C5—S1	−3.1 (4)	C17—N4—C16—S2	−3.5 (4)
C4—N1—C5—N2	−1.0 (4)	C15—N3—C16—N4	7.5 (4)
C4—N1—C5—S1	178.5 (2)	C15—N3—C16—S2	−173.7 (2)
C5—N2—C6—C7	110.5 (3)	C16—N4—C17—C22	−97.0 (3)
C5—N2—C6—C11	−71.0 (4)	C16—N4—C17—C18	83.5 (3)
C11—C6—C7—C8	0.3 (5)	C22—C17—C18—C19	−0.4 (5)
N2—C6—C7—C8	178.8 (3)	N4—C17—C18—C19	179.1 (3)
C6—C7—C8—C9	0.2 (5)	C17—C18—C19—C20	0.3 (5)
C7—C8—C9—C10	−1.0 (6)	C18—C19—C20—C21	0.0 (6)
C8—C9—C10—C11	1.3 (6)	C19—C20—C21—C22	−0.1 (6)
C7—C6—C11—C10	0.1 (5)	C18—C17—C22—C21	0.2 (5)
N2—C6—C11—C10	−178.5 (3)	N4—C17—C22—C21	−179.3 (3)
C9—C10—C11—C6	−0.8 (5)	C20—C21—C22—C17	0.0 (5)

Hydrogen-bond geometry (Å, º) top

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

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	2.04	2.701 (3)	134
N4—H4···O2	0.86	2.03	2.692 (3)	133
C3—H3A···Cl1	0.97	2.75	3.194 (3)	109
C14—H14B···Cl2	0.97	2.77	3.180 (3)	106
N1—H1···S2ⁱ	0.86	2.53	3.382 (2)	173
N2—H2···O2ⁱⁱ	0.86	2.40	3.142 (3)	144
N3—H3···S1ⁱⁱⁱ	0.86	2.58	3.439 (2)	175
N4—H4···O1ⁱⁱ	0.86	2.32	3.057 (3)	143
C14—H14A···S2^iv	0.97	2.73	3.676 (3)	166
C2—H2A···Cg2ⁱⁱ	0.97	2.80	3.419 (4)	123
C13—H13A···Cg1ⁱⁱ	0.97	2.83	3.417 (3)	153

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, y+1/2, −z+1/2; (iv) −x, −y+1, −z.

Experimental details

Crystal data
Chemical formula	C₁₁H₁₃ClN₂OS
M_r	256.74
Crystal system, space group	Monoclinic, P2₁/c
Temperature (K)	298
a, b, c (Å)	14.610 (3), 10.244 (2), 18.230 (4)
β (°)	112.408 (4)
V (Å³)	2522.5 (9)
Z	8
Radiation type	Mo Kα
µ (mm⁻¹)	0.45
Crystal size (mm)	0.50 × 0.49 × 0.09

Data collection
Diffractometer	Bruker SMART APEX CCD area-detector diffractometer
Absorption correction	Multi-scan (SADABS; Bruker, 2000)
T_min, T_max	0.807, 0.961
No. of measured, independent and observed [I > 2/s(I)] reflections	14531, 4706, 3195
R_int	0.043
(sin θ/λ)_max (Å⁻¹)	0.606

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.048, 0.131, 1.02
No. of reflections	4706
No. of parameters	289
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.48, −0.29

Computer programs: SMART (Bruker, 2000), SAINT (Bruker, 2000), SHELXS97 (Sheldrick, 2008), SHELXL97 (Sheldrick, 2008), SHELXTL (Sheldrick, 2008), SHELXTL, PARST (Nardelli, 1995) and PLATON (Spek, 2009).

Hydrogen-bond geometry (Å, º) top

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

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2···O1	0.86	2.04	2.701 (3)	134
N4—H4···O2	0.86	2.03	2.692 (3)	133
N1—H1···S2ⁱ	0.86	2.53	3.382 (2)	173
N2—H2···O2ⁱⁱ	0.86	2.40	3.142 (3)	144
N3—H3···S1ⁱⁱⁱ	0.86	2.58	3.439 (2)	175
N4—H4···O1ⁱⁱ	0.86	2.32	3.057 (3)	143
C14—H14A···S2^iv	0.97	2.73	3.676 (3)	166
C2—H2A···Cg2ⁱⁱ	0.97	2.80	3.419 (4)	123
C13—H13A···Cg1ⁱⁱ	0.97	2.83	3.417 (3)	153

Symmetry codes: (i) −x+1, y−1/2, −z+1/2; (ii) −x+1, −y+1, −z+1; (iii) −x+1, y+1/2, −z+1/2; (iv) −x, −y+1, −z.

Acknowledgements

The authors thank the Ministry of Higher Education of Malaysia and both Universiti Kebangsaan Malaysia and Universiti Malaysia Terengganu for the research grants UKM-GUP-NBT-08–27-110 and 59166, respectively.

References

Allen, F. H., Kennard, O., Watson, D. G., Brammer, L., Orpen, A. G. & Taylor, R. (1987). J. Chem. Soc. Perkin Trans. 2, pp. S1–19. CrossRef Web of Science Google Scholar
Bruker (2000). SADABS, SMART and SAINT. Bruker AXS Inc., Madison, Wisconsin, USA. Google Scholar
Figueiredo, I. M., Santos, L. V., Costa, W. F., Carvalho, J. E., Silva, C. C., Sacoman, J. L., Kohn, L. K. & Sarragiotto, M. H. (2006). J. Braz. Chem. Soc. 17, 954–960. Web of Science CrossRef CAS Google Scholar
Nardelli, M. (1995). J. Appl. Cryst. 28, 659. CrossRef IUCr Journals Google Scholar
Othman, E. A., Soh, S. K. C. & Yamin, B. M. (2010). Acta Cryst. E66, o628. Web of Science CSD CrossRef IUCr Journals Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar
Spek, A. L. (2009). Acta Cryst. D65, 148–155. Web of Science CrossRef CAS IUCr Journals Google Scholar
Sun, C., Huang, H., Feng, M., Shi, X., Zhang, X. & Zhaou, P. (2006). Bioorg. Med. Chem. Lett. 16, 162–166. Web of Science CrossRef PubMed CAS Google Scholar

This is an open-access article distributed under the terms of the Creative Commons Attribution (CC-BY) Licence, which permits unrestricted use, distribution, and reproduction in any medium, provided the original authors and source are cited.

CRYSTALLOGRAPHIC
COMMUNICATIONS

ISSN: 2056-9890

Volume 67| Part 2| February 2011| Page o419

doi:10.1107/S1600536811001498

Open

access