1-(4-Bromo­phen­yl)-1-(4-nitro­benzo­yl)thio­urea

Sohail Saeed; Naghmana Rashid; Arifa Tahir; Peter G Jones

doi:10.1107/S1600536809025884

. 2009 Jul 15;65(Pt 8):o1870–o1871. doi: 10.1107/S1600536809025884

1-(4-Bromophenyl)-1-(4-nitrobenzoyl)thiourea

Sohail Saeed ^a,^*, Naghmana Rashid ^a, Arifa Tahir ^b, Peter G Jones ^c

PMCID: PMC2977201 PMID: 21583565

Abstract

The title compound, C₁₄H₁₀BrN₃O₃S, crystallizes as two concomitant polymorphs that differ in colour (one yellow and one colourless). Only the structure of the colourless form could be determined. The molecule exists in the thioamide form with an intramolecular N—H⋯O=C hydrogen bond across the thiourea system. Molecules are linked into layers parallel to (120) by Br⋯O_nitro contacts [3.103 (1) Å], classical hydrogen bonds from the other NH function to the S atom and N_nitro⋯O=C contacts. The layers are linked by weak C—H⋯O_nitro hydrogen bonds to produce the observed three-dimensional network.

Related literature

For general background to thiourea complexe, see: Ugur et al. (2006 ▶). For the biological activity of thiourea derivatives, see: Glasser & Doughty (1964 ▶); Huebner et al. (1953 ▶); Manjula et al. (2009 ▶); Zheng et al. (2004 ▶). For related structures, see: Saeed et al. (2008a ▶,b ▶,c ▶).

Experimental

Crystal data

C₁₄H₁₀BrN₃O₃S
M _r = 380.22
Triclinic,
a = 7.0112 (3) Å
b = 8.9697 (5) Å
c = 11.9693 (6) Å
α = 87.386 (5)°
β = 75.044 (4)°
γ = 87.511 (4)°
V = 726.08 (6) Å³
Z = 2
Mo Kα radiation
μ = 2.99 mm⁻¹
T = 100 K
0.3 × 0.2 × 0.2 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis Pro; Oxford Diffraction, 2009 ▶) T _min = 0.945, T _max = 1.000 (expected range = 0.520–0.550)
24890 measured reflections
4234 independent reflections
3438 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.022
wR(F ²) = 0.051
S = 0.96
4234 reflections
207 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.81 e Å⁻³
Δρ_min = −0.80 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/S1600536809025884/im2125sup1.cif

e-65-o1870-sup1.cif^{(20.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809025884/im2125Isup2.hkl

e-65-o1870-Isup2.hkl^{(207.5KB, 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⋯O1	0.82 (1)	2.03 (2)	2.688 (2)	138 (2)
N2—H02⋯Sⁱ	0.77 (1)	2.79 (1)	3.553 (1)	169 (1)
C5—H5⋯O3ⁱⁱ	0.95	2.38	3.293 (2)	162
C3—H3⋯Sⁱⁱⁱ	0.95	2.93	3.474 (2)	118
C14—H14⋯Sⁱ	0.95	2.89	3.167 (1)	98
C14—H14⋯Br^iv	0.95	3.15	3.899 (1)	137

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

Acknowledgments

We are indebted to Dr Rizwan Hussain, Director of Chemical & Power Sources, National Development Complex, Pakistan, for providing facilities for the spectroscopic analysis.

supplementary crystallographic information

Comment

Industrial production and the use of elements such as Fe, Co, Cu, Ni, Zn, Cd and Pb can cause environmental pollution. However, some of these metals are present in trace amounts as essential elements for biological systems and also play an important role in bioinorganic chemistry. In order to understand the role of these metal ions in biological systems, structural studies of biological compounds and their metal complexes are extremely important. Compounds containing carbonyl and thiocarbonyl groups occupy an important position among organic reagents as potential donor ligands for transition metal ions (Ugur et al., 2006).

Thioureas are also known to exhibit a wide range of biological effects including antiviral, antibacterial, anticancer (Manjula et al., 2009), antifungal, antitubercular, antithyroidal, herbicidal and insecticidal activities (Huebner et al., 1953) and are used as agrochemicals (Saeed et al., 2008a<i/>). An example is furnished by 1-benzoyl-3-(4,5-disubstituted-pyrimidine-2-yl)- thioureas that have excellent herbicidal activity (Zheng et al., 2004). Thioureas are also well known chelating agents for transition metals (Saeed et al., 2008b<i/>). The complexes of thiourea derivatives also show varied biological activities (Glasser et al., 1964). Thioureas and substituted thioureas are also known as epoxy resin curing agents (Saeed et al., 2008b<i/>). We became interested in the synthesis of N-aroyl, N'-arylthioureas as intermediates towards some new heterocyclic compounds and for the systematic study of their bioactive complexes and their function as epoxy resin curing agents, and have recently published three structures from this compound class (Saeed et al., 2008a,b,c).

The molecule of the title compound is shown in Fig. 1. It crystallizes in the thioamide form with an intramolecular hydrogen bond N1—H01···O1. Bond lengths and angles may be regarded as normal. The central moiety N1—C7( S)—N2—C8(O1) is essentially planar (mean deviation 0.09 Å) and subtends interplanar angles of 38.42 (4)° and 56.27 (4)° with the aromatic rings at C1 and C9, respectively. This is also reflected by the corresponding torsion angles C7—N1—C1—C6 43.7 (2)° and N2—C8—C9—C14 - 50.8 (2)°.

The molecular packing is determined by a variety of intermolecular contacts. The molecules are linked to chains parallel to [211] by the halogen bond Br···O2 3.103 (1) Å, with an angle C4—Br···O2 of 176.07 (5)° (operator: x - 2, y + 1, z + 1). The chains are crosslinked by the classical H bond N2—H02···S (Table 1) and the contact N3···O1 2.957 (1) Å, with an angle C12—N3···O1 of 88.60 (7)° (operator: -x + 1, -y + 1, -z), to form layers parallel to (120). The layers are connected by the weak H bond C5—H5···O3 to give the observed three dimensionial structure (Table 1). Further borderline H···X interactions are also listed in Table 1 for the sake of completeness but are probably of minimal structural relevance.

Experimental

A solution of 4-nitrobenzoyl chloride (0.1 mol) in dry acetone (80 ml) was added dropwise to a suspension of ammonium thiocyanate (0.1 mol) in acetone (50 ml) and the reaction mixture was refluxed for 30 minutes. After cooling to room temperature, a solution of 4-bromoaniline (0.1 mol) in acetone (25 ml) was added and the resulting mixture refluxed for 1.5 h. The reaction mixture was poured into five times its volume of cold water, upon which the thiourea precipitated. The product was recrystallized from ethyl acetate as intensely yellow crystals. However, these crystals, despite near-perfect optical appearance under the microscope, proved to be unusable for X-ray analysis because their diffraction patterns were very weak and diffuse. A few large colourless prisms were therefore selected from the same sample and proved to be of diffraction quality. Clearly the title compound is polymorphic, and one may speculate that the different colours may arise from different H bonding patterns.