1-(4-Chloro­benzo­yl)-3-(3-methyl­pyridin-2-yl)thio­urea

MSukeri M Yusof; Nurwahyuni A Mushtari; Maisara A Kadir; Bohari M Yamin

doi:10.1107/S1600536811032375

. 2011 Aug 17;67(Pt 9):o2367. doi: 10.1107/S1600536811032375

1-(4-Chlorobenzoyl)-3-(3-methylpyridin-2-yl)thiourea

MSukeri M Yusof ^a,^*, Nurwahyuni A Mushtari ^a, Maisara A Kadir ^a, Bohari M Yamin ^b

PMCID: PMC3200797 PMID: 22058973

Abstract

The molecule of the title compound, C₁₄H₁₂ClN₃OS, consists of three approximately planar fragments: the central thiourea group, the chlorophenyl group and the picolyl (3-methylpyridin-2-yl) group with a maximum of 0.035 (2)° for an N atom from the mean square plane of the central thiourea group. The central fragment forms dihedral angles of 33.30 (8) and 76.78 (8)° with the chlorophenyl and picolyl groups, respectively. With respect to the thiourea C—N bonds, the 4-chlorobenzoyl group is positioned trans to the thiono S atoms, whereas the picolyl group lies in a cis position to it. The molecular conformation is stabilized by an intramolecular N—H⋯O hydrogen bond. In the crystal, molecules are linked by intermolecular C—H⋯N hydrogen bonds, forming chains along the a axis.

Related literature

For applications of thiourea derivatives, see: Cunha et al. (2007 ▶); Srivastava et al. (2010 ▶); Manjula et al. (2009 ▶); Chen et al. (2006 ▶). For related structures, see: Estévez-Hernández et al. (2009 ▶); Binzet et al. (2009 ▶). For standard bond lengths, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₄H₁₂ClN₃OS
M _r = 305.78
Monoclinic,
a = 7.8417 (15) Å
b = 7.1058 (13) Å
c = 25.585 (5) Å
β = 93.405 (4)°
V = 1423.1 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 298 K
0.44 × 0.31 × 0.14 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2003 ▶) T _min = 0.839, T _max = 0.944
9917 measured reflections
3421 independent reflections
2188 reflections with I > 2/s(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.053
wR(F ²) = 0.139
S = 1.04
3421 reflections
181 parameters
H-atom parameters constrained
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: SMART (Bruker, 2003 ▶); cell refinement: SAINT (Bruker, 2003 ▶); 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, PARST (Nardelli, 1995 ▶) and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811032375/yk2015sup1.cif

e-67-o2367-sup1.cif^{(21.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811032375/yk2015Isup2.hkl

e-67-o2367-Isup2.hkl^{(167.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811032375/yk2015Isup3.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
N2—H2A⋯O1	0.86	1.98	2.655 (2)	135
C2—H2B⋯N3ⁱ	0.93	2.59	3.417 (3)	148

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank the Malaysian Government, Universiti Kebangsaan Malaysia, Faculty of Science and Technology, Universiti Malaysia Terengganu and the Ministry of Higher Education, Malaysia, for research grants UKM-GUP-NBT-08–27–110 and FRGS 59178.

supplementary crystallographic information

Comment

The synthesis of new thiourea derivatives has attracted great interest because of their wide range applications in research and technology, such as in pharmacology (Cunha et al., 2007), catalysis (Chen et al., 2006) and agriculture (Srivastava et al., 2010). The title compound, (I), is an isomer of the previously reported compound, 4-chloro-N-[N-(6-methyl-2-pyridyl)-carbamothioyl]benzamide (Binzet et al., 2009) except the methyl group is attached at the third position of the pyridine ring. The molecule adopts trans-cis configuration with respect to the position of 4-chlorobenzoyl and 2-picolyl groups relative to the thiono S atom across the thiourea C—N bonds. The bond lengths and angles are within normal ranges (Allen et al., 1987) and agree with previously reported analogous molecules (Estévez-Hernández et al., 2009; Binzet et al., 2009). The molecule consists of central thiourea fragment (N2/C8/S1/N1), pyridine (C9—C13/N3) and phenyl (C1—C6) rings which are nearly planar with largest deviation from the least square plane of 0.035 (2)Å for N1 atom.

The molecule is stabilized by intramolecular hydrogen bond, O1···H2A—N2, forming a pseudo-six membered ring, O1···H2A—N2—C8—N1—C7—O1 (Table 1). In crystal the molecules are linked by intermolecular hydrogen bond C2—H2···N3ⁱ, forming chains along the a axis (Fig. 2).

Experimental

2-amino-3-picoline (1.0 g, 0.5 mmol) was added dropwise into the mixture of ammonium thiocyanate (0.62 g, 0.5 mmol) and 4-chlorobenzoyl chloride (0.44 g, 0.5 mmol) diluted by 50 ml of dry acetone. The reaction mixture was refluxed with permanent stirring for 3 h. The resulting precipitate was filtered off and washed with cold methanol. The colorless crystals were obtained by recrystallization from acetonitrile. Yield: 46%; m.p. 170.1–171.1°C