N-(2-Chloro­benzo­yl)-N′-(3-pyrid­yl)thio­urea

Lan-Qin Chai; Yu-Jie Ding; Xiao-Qing Yang; Hai-Bo Yan; Wen-Kui Dong

doi:10.1107/S1600536808019922

. 2008 Jul 5;64(Pt 8):o1407. doi: 10.1107/S1600536808019922

N-(2-Chlorobenzoyl)-N′-(3-pyridyl)thiourea

Lan-Qin Chai ^a, Yu-Jie Ding ^b, Xiao-Qing Yang ^a, Hai-Bo Yan ^a, Wen-Kui Dong ^a,^*

PMCID: PMC2962040 PMID: 21203127

Abstract

In the molecule of the title compound, C₁₃H₁₀ClN₃OS, the dihedral angles between the plane through the thiourea group and the pyridine and benzene rings are 53.08 (3) and 87.12 (3)°, respectively. The molecules are linked by intermolecular N—H⋯N hydrogen-bonding interactions to form a supramolecular chain structure along the a axis. An intramolecular N—H⋯O hydrogen bond is also present.

Related literature

For related literature, see: Campo et al. (2002 ▶); Dong et al. (2006 ▶, 2008 ▶); Foss et al. (2004 ▶); Guillon et al. (1996 ▶); Koch (2001 ▶); Krepps et al. (2001 ▶); Su et al. (2004 ▶, 2006 ▶); Teoh et al. (1999 ▶); Venkatachalam et al. (2004 ▶); West et al. (2000 ▶); Xian et al. (2004 ▶).

Experimental

Crystal data

C₁₃H₁₀ClN₃OS
M _r = 291.75
Triclinic,
a = 8.421 (3) Å
b = 9.282 (4) Å
c = 10.512 (4) Å
α = 98.336 (4)°
β = 110.797 (4)°
γ = 112.532 (4)°
V = 670.9 (5) Å³
Z = 2
Mo Kα radiation
μ = 0.43 mm⁻¹
T = 298 (2) K
0.32 × 0.11 × 0.07 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.874, T _max = 0.972
3504 measured reflections
2319 independent reflections
1734 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.036
wR(F ²) = 0.100
S = 1.02
2319 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.20 e Å⁻³
Δρ_min = −0.18 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808019922/rz2227sup1.cif

e-64-o1407-sup1.cif^{(17.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808019922/rz2227Isup2.hkl

e-64-o1407-Isup2.hkl^{(113.9KB, 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
N2—H2⋯O1	0.86	1.98	2.671 (3)	137
N1—H1⋯N3ⁱ	0.86	2.08	2.886 (4)	157

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by the Foundation of the Education Department of Gansu Province (No. 0604-01) and the ’Qing Lan’ Talent Engineering Funds of Lanzhou Jiaotong University (No. QL-03-01 A), which are gratefully acknowledged.

supplementary crystallographic information

Comment

Thiourea and its substituted derivatives have attracted much attention because of their unique properties, such as the strong coordination ability (Su et al., 2004; Su et al., 2006; Xian et al., 2004; West et al., 2000). They are used as selective analytical reagents, especially for the determination of transition metals in complex interfering matrices (Koch, 2001; Foss et al., 2004). It has been shown that the redox properties of thiourea are markedly influenced by electronic factors (Guillon et al., 1996), and the biological activity of thiourea derivatives has also been reported in the literature (Teoh et al., 1999; Campo et al., 2002). However, the study of S···H interactions may have fundamental importance in biochemical research due to the fact that living systems contain several important sulfur-containing molecules, such as the aminoacids cysteine and methionine (Krepps et al., 2001). Related to the biological relevance of S···H interactions, Uckum and coworkers have recently reported a structural study of a series of thiourea compounds (Venkatachalam et al., 2004). Here we report the synthesis and crystal structure of a new benzoylthiourea derivative, N-(o-chloro)benzoyl-N'-(3-pyridyl)thiourea. The molecular structure of the title compound is shown in Figure 1.

The dihedral angles formed by the plane through the thiourea group and the pyridine and benzene rings of 53.08 (3) and 87.12 (3)°, respectively. The molecular conformation is stabilized by an intramolecular N—H···O hydrogen bonding interaction (Table 1), forming a planar six-membered ring. In contrast to other thiourea compounds, the H1···S1 separation is 2.662 (2) Å, indicating that S1 is not involved in hydrogen bonding. This situation is similar to that found in the structure of N-benzoyl-N'-(3-pyridyl)thiourea (Dong et al., 2006). The C=O bond length of 1.217 (3) Å is just significantly longer than the average C=O bond length (1.200 Å) due to the intramolecular hydrogen bond. In the crystal structure, molecules are linked by intermolecular by N—H···N hydrogen interactions to form supramolecular chains along the a axis.

Experimental

N-(o-Chloro)benzoyl-N'-(3-pyridyl)thiourea was synthesized according the method reported in the literature (Dong et al., 2008). o-Chlorobenzoyl chloride (3.61 g, 0.02 mol) was reacted with ammonium thiocyanate (2.28 g, 0.03 mol) in CH₂Cl₂ (25 ml) under solid-liquid phase transfer catalysis, using 3% polyethylene glycol-400 (0.36 g) as catalyst, to give the corresponding benzoyl isothiocyanate, which was reacted with 3-aminopyridine (1.72 g, 0.02 mol). The title compound precipitated immediately. The product was filtered, washed with water and CH₂Cl₂ and dried. Colourless needle-shaped single crystals were obtained by slow evaporation of an acetone solution after several weeks at room temperature. M.p. 442 - 444 K. Anal. Calcd. for C₁₃H₁₀ClN₃OS: C, 53.52; H, 3.45; N, 14.40. Found: C, 53.28; H, 3.48; N, 14.15%.