1-Benzoyl-3-(2,4,5-trichloro­phen­yl)thio­urea

M Khawar Rauf; Masahiro Ebihara; Amin Badshah; Imtiaz-ud-Din

doi:10.1107/S1600536811052780

. 2011 Dec 14;68(Pt 1):o119. doi: 10.1107/S1600536811052780

1-Benzoyl-3-(2,4,5-trichlorophenyl)thiourea

M Khawar Rauf ^a,^*, Masahiro Ebihara ^b, Amin Badshah ^a, Imtiaz-ud-Din ^a

PMCID: PMC3254466 PMID: 22259406

Abstract

The benzene and phenyl rings in the title compound, C₁₄H₉Cl₃N₂OS, form a dihedral angle of 40.98 (6)°. The molecule exists in the thione form with typical thiourea C—S [1.666 (2) Å] and C—O [1.227 (3) Å] bond lengths as well as shortened C—N bonds [1.345 (3) and 1.386 (2) Å]. An intramolecular N—H⋯O hydrogen bond stabilizes the molecular conformation. In the crystal, pairs of N—H⋯S hydrogen bonds link the molecules into centrosymmetric dimers.

Related literature

For information on thiourea derivatives, see: Patil & Chedekel (1984 ▶); Baily et al. (1996 ▶); Namgun et al. (2001 ▶); Koch (2001 ▶); Wegner et al. (1986 ▶); Krishnamurthy et al. (1999 ▶); Murtaza et al. (2009a ▶,b ▶). For related structures, see: Khawar Rauf et al. (2009a ▶,b ▶). For bond-length data, see: Allen et al. (1987 ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C₁₄H₉Cl₃N₂OS
M _r = 359.64
Monoclinic,
a = 33.111 (8) Å
b = 3.8413 (7) Å
c = 25.220 (6) Å
β = 115.995 (2)°
V = 2883.1 (11) Å³
Z = 8
Mo Kα radiation
μ = 0.78 mm⁻¹
T = 296 K
0.20 × 0.20 × 0.20 mm

Data collection

Rigaku/MSC Mercury CCD diffractometer
Absorption correction: multi-scan (REQAB; Rigaku, 1998 ▶) T _min = 0.800, T _max = 1.000
11264 measured reflections
3264 independent reflections
2686 reflections with I > 2σ(I)
R _int = 0.039

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.084
S = 1.06
3264 reflections
190 parameters
H-atom parameters constrained
Δρ_max = 0.42 e Å⁻³
Δρ_min = −0.39 e Å⁻³

Data collection: CrystalClear (Molecular Structure Corporation and Rigaku, 2001 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SIR97 (Altomare et al., 1999 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶) and TEXSAN (Molecular Structure Corporation and Rigaku, 2004 ▶); software used to prepare material for publication: Yadokari-XG_2009 (Kabuto et al., 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811052780/bg2439sup1.cif

e-68-0o119-sup1.cif^{(17.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811052780/bg2439Isup2.hkl

e-68-0o119-Isup2.hkl^{(160.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811052780/bg2439Isup3.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
N1—H1⋯O1	0.86	1.89	2.586 (2)	137
N2—H2⋯S1ⁱ	0.86	2.83	3.6771 (19)	168

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Symmetry code: (i) Inline graphic .

Acknowledgments

MKR is grateful to the Quaid-i-Azam University, Islamabad, for financial support for a post-doctoral fellowship.

supplementary crystallographic information

Comment

Thiourea derivatives are very useful building blocks for the synthesis of a wide range of aliphatic macromolecular and heterocyclic compounds. Thus, benzothiazoles have been prepared from arylthioureas in the presence of bromine (Patil & Chedekel, 1984), 2-aminothiazoles from the condensation of thiourea with α-halocarbonyl compounds (Baily et al., 1996), and 2-Methyl-aminothiazolines from N-(2-hydroxyethyl)-N'-methylthioureas (Namgun et al., 2001). N, N-dialkyl-N-aroylthioureas have been efficiently used for the extraction of Nickle, Palladium and Platinum metals (Koch, 2001). Aliphatic and acylthioureas are well known for their antimicrobial activities (Wegner et al., 1986). Symmetrical and unsymmetrical thioureas have shown antifungal activity against the plant pathogens (Krishnamurthy et al., 1999). We became interested in the synthesis of these thioureas as intermediates in the synthesis of novel guanidines(Murtaza et al., 2009a ; 2009b) and heterocyclic compounds for the systematic study of bioactivity and Complexation behaviour. Hence, we present here the crystal structure of the title compound, (I), Fig. 1. Comparison with N-benzoyl-N'-phenylthioureas [Cambridge Structural Database (Mogul Version 1.7; Allen, 2002) and (Allen et al., 1987)], show the molecule to exist in the thione form with typical thiourea C—S and C—O bonds, as well as shortened C—N bond lengths. Comparison with N-benzoyl-N'-phenylthioureas (Khawar Rauf et al., 2009a,b) suggests the 2,4,5-trichloro substitution on phenyl ring implies no significant effect on these bond lengths. Compound (I) (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 C1—N2—C2—O1 [-5.0 (3)] and N1—C1—N2—C2 [1.7 (3)]. This is associated with the expected typical thiourea intramolecular N—H···O H–bond (Table 1), forming a six-membered ring commonly observed in this class of compounds (Khawar Rauf et al., 2009a,b). The dihedral angles to the N1 C1 S1 N2 C2 O1 plane are 50.97 (4)° for the ring formed by C3 to C8 and 11.44 (7)° for the ring formed by C9 to C14. The crystal packing shows intramolecular N—H···O and intermolecular N—H···S H–bonds (Table 1, Fig. 2). The Cl atoms are not involved in any type of H–bonds.

Experimental

Freshly prepared benzoylisothiocyanate (1.63 g, 10 mmol) was dissolved in acetone (50 ml) and stirred for 45 minutes. Afterwards neat 2,4,5-trichloroaniline(1.96 g, 10 mmol) was added and the resulting mixture was stirred for 1 h. The reaction mixture was then poured into acidified water and stirred well. The solid product was separated and washed with deionized water and purified by recrystallization from methanol/1,1-dichloromethane (1:1 v/v) to give fine crystals of the title compound (I), with an overall yield of 95%. Full spectroscopic and physical characterization will be reported elsewhere.