1-(4-Chloro­benzo­yl)-3-(2,4,6-trichloro­phen­yl)thio­urea hemihydrate

M Khawar Rauf; Michael Bolte; Amin Badshah

doi:10.1107/S1600536808041251

. 2008 Dec 17;65(Pt 1):o143. doi: 10.1107/S1600536808041251

1-(4-Chlorobenzoyl)-3-(2,4,6-trichlorophenyl)thiourea hemihydrate

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

PMCID: PMC2968059 PMID: 21581602

Abstract

The asymmetric unit of the title compound, C₁₄H₈Cl₄N₂OS·0.5H₂O, contains two independent molecules with different conformations with respect to the aromatic ring planes, and one water molecule. The bond lengths and angles are typical of thiourea compounds of this class. The molecule exists in the solid state in its thione form with typical thiourea C—S and C—O bonds lengths, as well as shortened C—N bonds. The dihedral angles between the two aromatic planes are 66.93 (8) and 60.44 (9)° in the two independent molecules. An intramolecular N—H⋯O hydrogen bond stabilizes the molecular conformation and the crystal packing is characterized by N—H⋯O, O—H⋯S and O—H⋯Cl hydrogen bonds.

Related literature

For background and related structures, see: Khawar Rauf et al. (2006a ▶,b ▶,c ▶,d ▶). For a description of the Cambridge Structural Database, see: Allen (2002 ▶).

Experimental

Crystal data

C₁₄H₈Cl₄N₂OS·0.5H₂O
M _r = 403.09
Monoclinic,
a = 16.1428 (9) Å
b = 13.7340 (7) Å
c = 16.2850 (9) Å
β = 112.216 (4)°
V = 3342.4 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.84 mm⁻¹
T = 173 (2) K
0.38 × 0.37 × 0.35 mm

Data collection

STOE IPDS II two-circle-diffractometer
Absorption correction: multi-scan (MULABS; Spek, 2003 ▶; Blessing, 1995 ▶) T _min = 0.741, T _max = 0.758
23391 measured reflections
7172 independent reflections
5964 reflections with I > 2σ(I)
R _int = 0.068

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.125
S = 1.02
7172 reflections
428 parameters
7 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.94 e Å⁻³
Δρ_min = −0.60 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/S1600536808041251/si2141sup1.cif

e-65-0o143-sup1.cif^{(25.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808041251/si2141Isup2.hkl

e-65-0o143-Isup2.hkl^{(351KB, 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⋯O1W	0.866 (10)	2.211 (17)	2.997 (3)	151 (3)
N2—H2⋯O1	0.873 (10)	1.97 (2)	2.627 (2)	131 (3)
N2—H2⋯O1Aⁱ	0.873 (10)	2.26 (2)	2.931 (3)	133 (2)
N1A—H1A⋯O1W	0.874 (10)	1.964 (13)	2.816 (3)	164 (3)
N2A—H2A⋯O1A	0.877 (10)	1.98 (3)	2.637 (3)	130 (3)
N2A—H2A⋯O1ⁱⁱ	0.877 (10)	2.31 (2)	3.001 (3)	136 (3)
O1W—H1WA⋯S1A	0.855 (10)	2.67 (3)	3.215 (2)	123 (3)
O1W—H1WA⋯Cl3ⁱⁱⁱ	0.855 (10)	2.84 (3)	3.388 (2)	123 (3)
O1W—H1WB⋯S1	0.855 (10)	2.36 (2)	3.091 (2)	144 (3)

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

Acknowledgments

MKR is grateful to the HEC-Pakistan for financial support for the PhD program 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, 2006b, 2006c, 2006d). Herein, as a continuation of these studies, the structure of the title compound (I) is described. A depiction of the two independent molecules is given in Fig. 1.The water molecule links the molecules through O_W—H···S and N—H···O_W hydrogen bonds. 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. An intramolecular N—H···O hydrogen bond is present, forming a six membered ring commonly observed in this class of compounds (Khawar Rauf et al., 2006a). The the crystal packing is stabilized by intermolecular N—H···O, O—H···S and O—H···Cl hydrogen bonds (Table 1).

Experimental

Freshly prepared 4-chlorobenzoyl isothiocyanate (2.0 g, 10 mmol) was stirred in acetone (40 ml) for 15 minutes. Neat 3,5-dichloroaniline (1.62 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%. Full spectroscopic and physical characterization will be reported elsewhere.