1-(4-Chloro­phen­yl)-3-(2,4-dichloro­benzo­yl)thio­urea

M Khawar Rauf; Michael Bolte; Amin Badshah

doi:10.1107/S160053680900004X

. 2009 Jan 8;65(Pt 2):o260. doi: 10.1107/S160053680900004X

1-(4-Chlorophenyl)-3-(2,4-dichlorobenzoyl)thiourea

M Khawar Rauf ^a,^*, Michael Bolte ^b, Amin Badshah ^a

PMCID: PMC2968241 PMID: 21581875

Abstract

The title compound, C₁₄H₉Cl₃N₂OS, has bond lengths and angles which are quite typical for thiourea compounds of this class. The molecule exists in the solid state in its thione form with typical thiourea C=S and C=O bond lengths, as well as shortened C—N bonds. An intramolecular N—H⋯O hydrogen bond stabilizes the molecular conformation. Intermolecular N—H⋯S hydrogen bonds link the molecules to form centrosymmetric dimers.

Related literature

For thiourea derivatives with biological activities, see: Baily et al. (1996 ▶); Koch (2001 ▶); Maryanoff et al. (1986 ▶); Namgun et al. (2001 ▶); Patil & Chedekel (1984 ▶); Upadlgaya & Srivastava (1982 ▶); Wegner et al. (1986 ▶); Krishnamurthy et al. (1999 ▶). For related structures, see: Khawar Rauf et al. (2006a ▶,b ▶,c ▶, 2007 ▶). For standard bond-length data, see: Allen (2002 ▶).

Experimental

Crystal data

C₁₄H₉Cl₃N₂OS
M _r = 359.65
Triclinic,
a = 5.9674 (6) Å
b = 9.6577 (9) Å
c = 13.9585 (13) Å
α = 92.919 (6)°
β = 98.005 (7)°
γ = 101.330 (8)°
V = 778.54 (13) Å³
Z = 2
Mo Kα radiation
μ = 0.72 mm⁻¹
T = 173 (2) K
0.37 × 0.34 × 0.33 mm

Data collection

Stoe IPDS II two-circle diffractometer
Absorption correction: multi-scan (MULABS; Spek, 2003 ▶; Blessing, 1995 ▶) T _min = 0.776, T _max = 0.797
10758 measured reflections
3418 independent reflections
3154 reflections with I > 2σ(I)
R _int = 0.037

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.078
S = 1.02
3418 reflections
199 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.35 e Å⁻³
Δρ_min = −0.30 e Å⁻³

Data collection: X-AREA (Stoe & Cie, 2001 ▶); cell refinement: X-AREA; data reduction: X-AREA; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP in SHELXTL-Plus (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S160053680900004X/rk2121sup1.cif

e-65-0o260-sup1.cif^{(17.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680900004X/rk2121Isup2.hkl

e-65-0o260-Isup2.hkl^{(167.6KB, 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—H1⋯S1ⁱ	0.84 (2)	2.71 (2)	3.4273 (12)	144.3 (16)
N2—H2⋯O1	0.81 (2)	2.06 (2)	2.7098 (16)	136.4 (19)

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Symmetry code: (i) Inline graphic .

Acknowledgments

MKR is grateful to the HEC, Pakistan, for financial support for a PhD programme under scholarship No. ILC-0363104.

supplementary crystallographic information

Comment

N-substituted and N,N'-disubstituted thiourea derivatives are very useful starting materials for the synthesis of a wide range of aliphatic macromolecular and heterocyclic compounds. Benzothiazoles have been prepared from arylthioureas in the presence of bromine (Patil & Chedekel, 1984) and condensation of thiourea with α-halocarbonyl compounds form 2-aminothiazoles (Baily et al., 1996). The 2-methyl-aminothiazolines have been synthesized by cyclization of N-(2-hydroxyethyl)-N'-methylthioureas (Namgun et al., 2001). Thioureas are efficient guanylating agents (Maryanoff et al., 1986). The N,N-dialkyl-N-aroylthioureas have been effectively used for the extraction of Ni, Pd and Pt metals (Koch, 2001). Aliphatic and acylthioureas are well known for their fungicidal, antiviral, pesticidal and plant-growth regulating activities (Upadlgaya & Srivastava, 1982; Wegner et al., 1986). Symmetrical and unsymmetrical thioureas have shown antifungal activity against the plant pathogens Pyricularia oryzae and Drechslera oryzae (Krishnamurthy et al., 1999). We are interested in the synthesis of these thioureas as intermediates in the synthesis of novel guanidines and heterocyclic compounds for the systematic study of bioactivity and complexation behaviour and we present here the crystal structure of the title compound. The title compound (Fig. 1) shows the typical thiourea C═S and C═O double bonds as well as shortened C—N bond lengths. The thiocarbonyl and carbonyl groups are almost coplanar, as reflected by the torsion angles C2—N1—C1—O1 = 9.0 (2)° and N2—C2—N1—C1 = 5.5 (2)°. This is associated with the expected typical thiourea intramolecular N—H···O hydrogen bond (Table). The dihedral angle formed by the two benzene ring planes is 9.35 (9)°. Bond lengths and angles can be regarded as typical for N,N'-disubstituted thiourea compounds as found in the Cambridge Structural Database ver. 5.28 (Allen, 2002) and Khawar Rauf et al., 2006a,b,c, 2007. Intermolecular N—H···S hydrogen bonds (Table, Fig. 2), link the molecules to dimers. The Cl atoms are not involved in any type of hydrogen bonds.

Experimental

Freshly prepared 2,4-dichlorobenzoyl isothiocyanate (2.3 g, 10 mmol) was stirred in acetone (40 ml) for 20 min. Neat 4-chloroaniline (1.3 g, 10 mmol) was then added and the resulting mixture was stirred for 1.5 h. The reaction mixture was then poured into acidified (pH 4) water and stirred well. The solid product was separated and washed with deionized water and purified by recrystallization from methanol–1,1-dichloromethane (1:10 v/v) to give fine crystals of title compound, with an overall yield of 90%. Full spectroscopic and physical characterization will be reported elsewhere.