1-(2,6-Dichloro­benzo­yl)-3-(2,3,5,6-tetra­chloro­phen­yl)thio­urea trichloro­methane hemisolvate

M Khawar Rauf; Michael Bolte; Saeed Anwar

doi:10.1107/S1600536809000051

. 2009 Jan 8;65(Pt 2):o249. doi: 10.1107/S1600536809000051

1-(2,6-Dichlorobenzoyl)-3-(2,3,5,6-tetrachlorophenyl)thiourea trichloromethane hemisolvate

M Khawar Rauf ^a,^*, Michael Bolte ^b, Saeed Anwar ^c

PMCID: PMC2968195 PMID: 21581865

Abstract

The title compound, C₁₄H₆Cl₆N₂OS·0.5CHCl₃, crystallizes with four 1-(2,6-dichlorobenzoyl)-3-(2,3,5,6-tetrachlorophenyl)thiourea molecules and two trichloromethane molecules in the asymmetric unit. The thiourea molecules exist in the solid state in their thione forms with typical thiourea C—S and C—O bonds lengths, as well as shortened C—N bonds. The —NH—C(=S)—NH—C(=O)— plane is almost perpendicular to the benzene ring in each thiourea molecule. Intramolecular N—H⋯O hydrogen bonds stabilize the molecular conformation and intermolecular N—H⋯S hydrogen bonds stabilize the packing arrangement.

Related literature

For related compounds, see: Khawar Rauf et al. (2006a ▶,b ▶, 2007 ▶). For standard bond-length data, see: Allen (2002 ▶).

Experimental

Crystal data

C₁₄H₆Cl₆N₂OS·0.5CHCl₃
M _r = 522.65
Monoclinic,
a = 26.7213 (6) Å
b = 8.6580 (2) Å
c = 36.1046 (9) Å
β = 110.683 (2)°
V = 7814.6 (3) Å³
Z = 16
Mo Kα radiation
μ = 1.20 mm⁻¹
T = 173 (2) K
0.43 × 0.41 × 0.38 mm

Data collection

Stoe IPDS II two-circle diffractometer
Absorption correction: multi-scan (MULABS; Spek, 2003 ▶; Blessing, 1995 ▶) T _min = 0.627, T _max = 0.659
156440 measured reflections
22452 independent reflections
17143 reflections with I > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.147
S = 1.08
22452 reflections
969 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.64 e Å⁻³
Δρ_min = −1.40 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/S1600536809000051/ez2154sup1.cif

e-65-0o249-sup1.cif^{(43.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000051/ez2154Isup2.hkl

e-65-0o249-Isup2.hkl^{(1.1MB, 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⋯S1B	0.80 (3)	2.60 (3)	3.362 (2)	160 (3)
N2—H2⋯O1	0.78 (3)	1.96 (3)	2.621 (2)	142 (3)
N2—H2⋯Cl4Cⁱ	0.78 (3)	2.94 (3)	3.539 (2)	135 (3)
N1A—H1A⋯S1C	0.84 (3)	2.55 (3)	3.381 (2)	170 (3)
N2A—H2A⋯O1A	0.75 (3)	2.00 (3)	2.625 (3)	141 (3)
N2A—H2A⋯Cl4Aⁱⁱ	0.75 (3)	2.90 (3)	3.478 (2)	136 (3)
N1B—H1B⋯S1	0.83 (3)	2.63 (3)	3.425 (2)	162 (3)
N2B—H2B⋯O1B	0.78 (3)	2.01 (3)	2.639 (2)	138 (3)
N1C—H1C⋯S1A	0.86 (3)	2.57 (3)	3.416 (2)	168 (3)
N2C—H2C⋯O1C	0.77 (3)	1.97 (3)	2.629 (3)	144 (3)

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

Acknowledgments

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

supplementary crystallographic information

Comment

The background to this study has been set out in our previous work on the structural chemistry of N,N'-disubstituted thioureas (Khawar Rauf et al., 2006a, 2007). Herein, as a continuation of these studies, the structure of the title compound (I) is described. A depiction of the molecule is given in Fig. 1. Bond lengths and angles can be regarded as typical for N,N'-disubstituted thiourea compounds as found in the Cambridge Structural Database v5.28 (Allen, 2002; Khawar Rauf et al., 2006b). The molecule exists in the thione form with typical thiourea C—S and C—O bonds, as well as shortened C—N bond lengths. The thiocarbonyl and carbonyl groups are almost coplanar. The molecule features an intramolecular N—H···O hydrogen bond (see the table of hydrogen bond geometry; Fig 2).

Experimental

Freshly prepared and steam distillated 2,6-dichlorobenzoyl isothiocyanate (2.32 g, 10 mmol) was stirred in acetone (50 ml) for 20 minutes. Neat 2,3,5,6-tetrachloroaniline (2.30 g, 10 mmol) was then added and the resulting mixture was stirred for 1 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 (I), with an overall yield of 85%.