N-Benzoyl-N′-(2-chloro-3-pyrid­yl)thio­urea

Yu-Jie Ding; Jian Yao; Jian-Chao Wu; Wen-Kui Dong; Jun-Feng Tong

doi:10.1107/S1600536809027081

. 2009 Jul 18;65(Pt 8):o1903. doi: 10.1107/S1600536809027081

N-Benzoyl-N′-(2-chloro-3-pyridyl)thiourea

Yu-Jie Ding ^a, Jian Yao ^b, Jian-Chao Wu ^b, Wen-Kui Dong ^b,^*, Jun-Feng Tong ^b

PMCID: PMC2977241 PMID: 21583593

Abstract

The title compound, C₁₃H₁₀ClN₃OS, was prepared by the reaction of 3-amino-2-chloropyridine with benzoyl isothiocyanate at room temperature. The thiourea group makes dihedral angles of 47.17 (5) and 51.88 (4)°, respectively, with the benzene and pyridyl rings, while the angle between the benzene and pyridine rings is 8.91 (3)°. Intermolecular hydrogen-bond interactions link neighbouring molecules into an infinite supramolecular structure.

Related literature

For the biological activities of benzanilide and its N-substituted derivatives, see: Teoh et al. (1999 ▶); Campo et al. (2002 ▶). For the functions of related chlorophenyl compounds, see: Saeed et al. (2008 ▶); Gowda et al. (2008a ▶,b ▶,c ▶). For an isomeric compound, see: Chai et al. (2008 ▶). For our previous work on thiourea and its derivatives, see: Dong et al. (2006 ▶, 2007 ▶, 2008a ▶,b ▶). For the synthetic procedure, see: Ding et al. (2008 ▶).

Experimental

Crystal data

C₁₃H₁₀ClN₃OS
M _r = 291.73
Monoclinic,
a = 3.9443 (4) Å
b = 14.9250 (15) Å
c = 22.268 (2) Å
β = 93.889 (1)°
V = 1307.9 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 298 K
0.41 × 0.20 × 0.18 mm

Data collection

Bruker SMART 1000 CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.839, T _max = 0.924
6459 measured reflections
2315 independent reflections
1661 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.088
S = 1.03
2315 reflections
172 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.21 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/S1600536809027081/at2841sup1.cif

e-65-o1903-sup1.cif^{(17.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809027081/at2841Isup2.hkl

e-65-o1903-Isup2.hkl^{(113.8KB, 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	1.94	2.633 (2)	137
N1—H1⋯S1ⁱ	0.86	2.74	3.5982 (18)	178
C12—H12⋯O1ⁱⁱ	0.93	2.70	3.324 (3)	125

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

Acknowledgments

The authors acknowledge financial support from the ‘Jing Lan’ Talent Engineering Funds of Lanzhou Jiaotong University and the Natural Science Foundation of the Department of Education, An-Hui Province (grant No. KJ2009B110).

supplementary crystallographic information

Comment

Benzanilide and its N-substituted derivatives have been considered to be a class of privileged structural compounds, which usually have excellent biological activities (Teoh et al., 1999; Campo et al., 2002). However, the literatures are full of the function of the 2-chloro-4-nitrophenyl (Saeed et al., 2008), 3,5-dichlorophenyl (Gowda et al., 2008a) and 3-chlorophenyl (Gowda et al., 2008b; Gowda et al., 2008c) and also structures of benzamide and related compounds. As an extension of our work (Dong et al., 2006; Dong et al., 2007; Dong et al., 2008a; Dong et al., 2008b) on synthesis and structural characterization of thiourea and its derivatives, here report the synthesis and structure of the title compound.

In the molecule of the title compound, N-benzoyl-N'-(2-chloro-3-pyridyl)thiourea (Fig. 1), which is isomeric compound to its observed in the structures of N-(2-chlorobenzoyl)-N'-(3-pyridyl)thiourea (Chai et al., 2008). The thiourea group makes dihedral angles of 47.17 (5)° and 51.88 (4)° with the benzene and pyridyl rings respectively, while the angle between the benzene and pyridine rings is 8.91 (3)°. The carbonyl group forms an intramolecular hydrogen bond with the N2—H2 group, which forms a six-membered ring (C2/N1/C1/N2/H2/O1) structure, the H2···O1 bond length is 1.94 Å. The C═O bond length with 1.218 (3) Å is longer than the average C═O bond length [1.200 Å], which is due to intramolecular hydrogen bonding. This is similar to the situation found in the structure of N-benzoyl-N'-(3-pyridyl)thiourea (Dong et al., 2006). The crystal structure is further stabilized by intermolecular N1—H1···S1 and C12—H12···O1 hydrogen bonds interactions (Table 1, Fig. 2), which link neighbouring molecules into an infinite supramolecular structure.

Experimental

N-Benzoyl-N'-(2-chloro-3-pyridyl)thiourea was synthesized according to an analogous method reported earlier (Ding et al., 2008). Benzoyl chloride (702.8 mg, 5.00 mmol) was reacted with ammonium thiocyanate (380.6 mg, 5.00 mmol) in acetonitrile solution (25 ml) continuring stirring for 3 h at room temperature, to give the corresponding benzoyl isothiocyanate, which was added 3-amino-2-chloropyrldine (642.8 mg, 5.00 mmol). After stirring for 20 h at room temperature, the precipitate was reduced pressure filtered, washed successively with acetonitrile and diethyl ether. The product was dried in vacuo, and obtained 599.2 mg of needle-like crystalline solid. Yield, 41.07%. m.p. 424–426 K. Colorless single crystals suitable for X-ray diffraction studies were obtained after two weeks by slow evaporation from a mixture of ethyl acetate/acetone (1:1) of N-benzoyl-N'-(2-chloro-3-pyridyl)thiourea at room temperture. Analysis calculated for C₁₃H₁₀ClN₃OS (%): C 53.52, H 3.45, N 14.40. Found: C 53.61, H 3.51, N 14.3.