1-(2-Bromo­phen­yl)-3-(4-chloro­butano­yl)thio­urea

Mohd Sukeri Mohd Yusof; Nur Farhana Embong; Suhana Arshad; Ibrahim Abdul Razak

doi:10.1107/S160053681201327X

. 2012 Mar 31;68(Pt 4):o1267. doi: 10.1107/S160053681201327X

1-(2-Bromophenyl)-3-(4-chlorobutanoyl)thiourea

Mohd Sukeri Mohd Yusof ^a, Nur Farhana Embong ^a, Suhana Arshad ^b, Ibrahim Abdul Razak ^b,^*,^‡

PMCID: PMC3344192 PMID: 22606195

Abstract

The asymmetric unit of the title compound, C₁₁H₁₂BrClN₂OS, consists of two crystallographically independent molecules. In each molecule, the butanoylthiourea unit is nearly planar, with maximum deviations of 0.1292 (19) and 0.3352 (18) Å from the mean plane defined by nine non-H atoms, and is twisted relative to the terminal benzene ring with dihedral angles of 69.26 (7) and 82.41 (7)°. An intramolecular N—H⋯O hydrogen bond generates an S(6) ring motif in each butanoylthiourea unit. In the crystal, N—H⋯O hydrogen bonds link the two independent molecules together, forming an R ₂ ²(12) ring motif. The molecules are further connected into a tape along the c axis via N—H⋯S and C—H⋯S hydrogen bonds.

Related literature

For related structures, see: Binzet et al. (2009 ▶); Khawar Rauf et al. (2006 ▶); Shoukat et al. (2007 ▶); Yesilkaynak et al. (2010 ▶); Yusof et al. (2007 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For stability of the temperature controller used in the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₁H₁₂BrClN₂OS
M _r = 335.65
Monoclinic,
a = 14.1384 (2) Å
b = 11.1948 (1) Å
c = 17.7264 (2) Å
β = 107.955 (1)°
V = 2669.03 (5) Å³
Z = 8
Mo Kα radiation
μ = 3.42 mm⁻¹
T = 100 K
0.39 × 0.17 × 0.11 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2009 ▶) T _min = 0.350, T _max = 0.696
34224 measured reflections
8749 independent reflections
6599 reflections with I > 2σ(I)
R _int = 0.029

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.067
S = 1.02
8749 reflections
307 parameters
H-atom parameters constrained
Δρ_max = 0.64 e Å⁻³
Δρ_min = −0.48 e Å⁻³

Data collection: APEX2 (Bruker, 2009 ▶); cell refinement: SAINT (Bruker, 2009 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S160053681201327X/is5098sup1.cif

e-68-o1267-sup1.cif^{(31.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681201327X/is5098Isup2.hkl

e-68-o1267-Isup2.hkl^{(428KB, hkl)}

Supplementary material file. DOI: 10.1107/S160053681201327X/is5098Isup3.cml

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

Table 1. Hydrogen-bond geometry (Å, °).

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1A—H1NA⋯O1A	0.84	2.01	2.6847 (19)	136
N1B—H1NB⋯O1B	0.84	1.97	2.6464 (19)	136
N1A—H1NA⋯O1B	0.84	2.33	2.9976 (18)	137
N1B—H1NB⋯O1A	0.84	2.39	3.0566 (19)	137
N2A—H2NA⋯S1Bⁱ	0.85	2.56	3.3931 (15)	168
N2B—H2NB⋯S1Aⁱⁱ	0.84	2.56	3.3928 (14)	171
C9B—H9BA⋯S1Aⁱⁱ	0.99	2.87	3.7237 (18)	145
C9B—H9BB⋯S1Bⁱⁱⁱ	0.99	2.84	3.7248 (18)	149

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

Acknowledgments

The authors thank the Malaysian Government, Universiti Malaysia Terengganu and Universiti Sains Malaysia for research facilities and the Fundamental Research Grant Scheme (FRGS) No. 203/PFIZIK/6711171 and FRGS 59178 to conduct this work.

supplementary crystallographic information

Comment

Thiourea derivatives are flexible ligand and able to coordinate to the metal centre as mono-dentat or multi-dentat depended on the substituent group attached to the both of nitrogen atoms (Binzet et al., 2009; Yesilkaynak et al., 2010).

The asymmetric unit of the title compound (Fig. 1), consists of two crystallographically independent molecules A and B. In both molecules, the intramolecular N1A—H1NA···O1A and N1B—H1NB···O1B hydrogen bonds (Table 1) generate S(6) ring motifs (Bernstein et al., 1995). The chlorobutanoylthiourea groups (Cl1A/S1A/O1A/N1A/N2A/C7A–C11A & Cl1B/S1B/O1B/N1B/N2B/C7B–C11B) are twisted about C10A–C11A bond with C9A–C10A–C11A–Cl1A torsion angle of -66.74 (19)° and about C10B–C11B bond with C9B–C10B–C11B–Cl1B torsion angle of 60.18 (19)°, respectively. However, the butanoylthiourea groups (S1A/O1A/N1A/N2A/C7A–C11A & S1B/O1B/N1B/N2B/C7B–C11B) are nearly planar with maximum deviations of 0.1292 (19) Å at atom C10A and 0.3352 (18) Å at atom C10B. The mean plane through the butanoylthiourea group of molecule A (S1A/O1A/N1A/N2A/C7A–C11A) makes a dihedral angle of 69.26 (7)° with the terminal benzene ring (C1A–C6A). In molecule B, the corresponding value is 82.41 (7)°. The bond lengths and angles are within normal ranges and are comparable to the related structures (Shoukat et al., 2007; Khawar Rauf et al., 2006; Yusof et al., 2007).

In the crystal packing (Fig. 2), intermolecular N—H···O hydrogen bonds (Table 1), form R²₂(12) (Bernstein et al.,1995) ring motifs. The molecules are further connected into a molecular tape along the c axis via intermolecular N—H···S and C—H···S hydrogen bonds (Table 1).

Experimental

An equimolar amount of 2-bromoaniline (1.22 g, 7.09 mmol) in 20 ml acetone was added drop-wise into a stirring acetone solution (75 ml) containing 4-chlorobutanoylchloride (1.00 g, 7.09 mmol) and ammonium thiocyanate (0.54 g, 7.09 mmol). The mixture was refluxed for 1 h. Then, the solution was filtered-off and left to evaporate at room temperature.