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

Sohail Saeed; Naghmana Rashid; Rizwan Hussain; Peter G Jones

doi:10.1107/S1600536809038537

. 2009 Sep 30;65(Pt 10):o2568–o2569. doi: 10.1107/S1600536809038537

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

Sohail Saeed ^a,^*, Naghmana Rashid ^a, Rizwan Hussain ^b, Peter G Jones ^c

PMCID: PMC2970465 PMID: 21578006

Abstract

The title compound, C₁₂H₉BrN₂OS₂, consists of two planar parts, viz. the thiophene 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 interplanar angle is 18.84 (6)°. An intramolecular C_phenyl—N—H⋯OC hydrogen bond is observed. The three-dimensional packing involves three types of interactions, 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 _r = 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
Δρ_max = 0.42 e Å⁻³
Δρ_min = −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.

Supplementary Material

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

e-65-o2568-sup1.cif^{(17.9KB, cif)}

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

e-65-o2568-Isup2.hkl^{(133.2KB, hkl)}

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
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

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

Acknowledgments

The authors are grateful to Allama Iqbal Open University and the National Engineering & Scientific Commission, Islamabad, Pakistan, for the allocation of research and analytical laboratory facilities.

supplementary crystallographic information

Comment

The development of new antimicrobial and anticancer therapeutic agents is one of the fundamental goals in medicinal chemistry. Cytotoxicity and genotoxicity of anticancer drugs to normal cells are major problems in cancer therapy and engender the risk of inducing secondary malignancy (Aydemir et al., 2003). A dose of an anticancer drug sufficient to kill tumor cells is often toxic to the normal tissue and leads to many side effects, which, in turn, limit the efficacy of treatment. In recent years, there has been a concerted search for novel selective antitumor agents that lack many of the unpleasant side effects of conventional agents. Thiourea and its derivatives have found extensive applications in the field of medicine, agriculture and analytical chemistry. They are known to exhibit a wide variety of biological activities such as antiviral, anti-bacterial, antifungal, anticancer, antitubercular, herbicidal and insecticidal effects, and also constitute some epoxy resin curing agents containing amino functional groups (Saeed et al., 2008a,b,c). They have found broad areas of application e.g. in anion recognition, nonlinear optics and catalysis, and also display good coordination ability (Choi et al., 2008; Jones et al., 2008; Su et al., 2006). As part of our research on thiourea coordination chemistry, we are interested in the study of the influence of non-covalent interactions, especially hydrogen bonds and π-π stacking interactions, on the coordination modes of benzothiazoles bearing the 4-nitrobenzoylthiourea group with transition metal ions. Such coordination compounds of thiourea have been studied for various biological systems in terms of their antibacterial, antifungal and anticancer activities (Yunus et al., 2008).The importance of such work lies in the possibility that the next generation of thiourea derivatives might be more efficacious as antimicrobial and anticancer agents. However, a thorough investigation of their structure, activity and stability under biological conditions is required. These detailed investigations could be helpful in designing more potent antimicrobial and anticancer agents for therapeutic use. The condensation of acyl/aroyl thiocyanates with primary amines affords 1,3-disubstituted thioureas in excellent yields in a single step. In the present paper, the crystal structure of the title compound is reported.

The molecule (Fig. 1) consists of two planar parts: the thiophene ring plus C5 (r.m.s. deviation 0.007 Å) and the phenyl ring plus Br,N2,C6,S2 (0.05 Å), which subtend an interplanar angle of 18.84 (6)°. An intramolecular hydrogen bond N2—H02···O is observed.

The molecular packing is determined by four intermolecular contacts, each of which involves one or other of the sulfur atoms: a surprisingly long classical H bond N1—H01···S2, two weak C—H···S interactions (Table 1) and an interaction C1—S1···Br—C10 with S1···Br 3.6924 (6) Å, C1—S1···Br 165.89 (7) ° and S1···Br—C10 90.51 (6)° (operator for Br and C10: -x + 1/2, y - 3/2, -z + 1/2). The combined effect is to create a three-dimensional pattern, a small part of which is shown in Fig. 2.

Experimental

A mixture of ammonium thiocyanate (26 mmol) and 2-thiophene carbonyl chloride (26 mmol) in anhydrous acetone (60 ml) was stirred for 45 min. 2-Bromoaniline (26 mmol) was added and the reaction mixture was refluxed for 2 h. After cooling, the reaction mixture was poured into acidified cold water. The resulting dark yellow solid was filtered and washed with cold acetone. The title compound (I) was obtained as colourless needles and laths of several mm length by recrystallization of the solid from ethyl acetate. These tended to split lengthwise when cut, but eventually a fragment suitable for X-ray structure analysis was found.