3-Chloro-N-(diphenyl­carbamothio­yl)benzamide

Gün Binzet; Ulrich Flörke; Nevzat Külcü; Hakan Arslan

doi:10.1107/S1600536809001639

. 2009 Jan 17;65(Pt 2):o351–o352. doi: 10.1107/S1600536809001639

3-Chloro-N-(diphenylcarbamothioyl)benzamide

Gün Binzet ^a, Ulrich Flörke ^b, Nevzat Külcü ^a, Hakan Arslan ^c,^d,^*

PMCID: PMC2968266 PMID: 21581951

Abstract

In the title compound, C₂₀H₁₅ClN₂OS, the bond lengths and angles in the thiourea group are typical of thiourea derivatives. The C—N bond lengths in the center of the molecule are shorter than the normal C—N single bond due to the resonance effects in this part of the molecule. The conformation of the title molecule with respect to the thiocarbonyl and carbonyl groups is twisted, as reflected by the C—N—C—O and C—N—C—N torsion angles of −4.4 (6) and −53.3 (5)°, respectively. Pairs of the molecules are linked into centrosymmetric dimers, stacked along the c axis via intermolecular N—H⋯S interactions. There are also weak intermolecular C—H⋯O and C—H⋯S contacts in the structure.

Related literature

For synthesis, see: Özer et al. (2009 ▶); Mansuroğlu et al. (2008 ▶); Uğur et al. (2006 ▶); Arslan et al. (2003c ▶). For general background, see: Koch (2001 ▶); Huebhr et al. (1953 ▶); Madan et al. (1991 ▶); Schroeder (1955 ▶). For related structures, see: Khawar Rauf et al. (2006 ▶, 2009 ▶); Arslan et al. (2003a ▶,b ▶); Yamin & Yusof (2003 ▶).

Experimental

Crystal data

C₂₀H₁₅ClN₂OS
M _r = 366.85
Triclinic,
a = 8.196 (5) Å
b = 10.357 (6) Å
c = 11.699 (6) Å
α = 72.565 (10)°
β = 70.495 (10)°
γ = 71.303 (10)°
V = 865.8 (9) Å³
Z = 2
Mo Kα radiation
μ = 0.35 mm⁻¹
T = 120 (2) K
0.49 × 0.32 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.847, T _max = 0.966
5401 measured reflections
3490 independent reflections
2290 reflections with I > 2σ(I)
R _int = 0.080

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.146
S = 1.06
3490 reflections
230 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809001639/bq2121sup1.cif

e-65-0o351-sup1.cif^{(19.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809001639/bq2121Isup2.hkl

e-65-0o351-Isup2.hkl^{(171.1KB, 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⋯S1ⁱ	0.90 (2)	2.48 (3)	3.351 (4)	162 (2)
C13—H13A⋯O1ⁱⁱ	0.95	2.59	3.434 (5)	148
C18—H18A⋯S1ⁱⁱⁱ	0.95	2.87	3.609 (5)	136

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

Acknowledgments

This work was supported by Mersin University Research Fund (Project Nos. BAP-ECZ-F-TBB-(HA) 2004–3 and BAPFEF-KB-(NK) 2006–3). This study is part of the PhD thesis of Gün Binzet.

supplementary crystallographic information

Comment

Thioureas and their metal complexes are an important class of compounds with a wide range of biological applications such as antitubercular, antithroid, anthelmintic, antibacterial, insecticidal and rodenticidal properties (Schroeder, 1955; Huebhr et al., 1953; Madan et al., 1991). Another area of the application of thiourea derivatives is analytical chemistry where some of these compounds have been used in the liquid-liquid extraction and separation of some transition metal ions (Koch, 2001).

Recently, a number of works on the structural and spectral properties of the thiourea derivatives and their metal complexes have appeared in the literature (Özer et al., 2009; Mansuroğlu et al., 2008; Uğur et al., 2006; Arslan et al., 2003c). We report here the crystal structure of one of them. The synthesis involves the reaction of a 3-chlorobenzoyl chloride with potassium thiocyanate in dry acetone followed by condensation of the 3-chlorobenzoyl isothiocyanate with the diphenylamine.

The molecular structure of the title compound, (I), is depicted in Fig. 1. The bond lengths and angles in the thiourea moiety are typical for thiourea derivatives; the C1-S1 (1.659 (3) Å) and C14-O1 (1.216 (4) Å) bonds both show typical double-bond character (Arslan et al., 2003a, 2003b; Khawar Rauf et al. 2009, 2006; Yamin & Yusof, 2003). The C-N bond lengths C14-N1 (1.388 (4) Å), C1-N1 (1.380 (4) Å) and C1-N2 (1.336 (4) Å) are shorter than the normal C-N single-bond length of about 1.48 Å. The shortening of these C-N bonds reveals the effects of resonance in this part of the molecule (Arslan et al., 2003a, 2003b; Khawar Rauf et al., 2009, 2006; Yamin & Yusof, 2003). The conformation of the title molecule with respect to the thiocarbonyl and carbonyl moieties is twisted, as reflected by the C1-N1-C14-O1 and C14-N1-C1-N2 torsion angles of -4.4 (6) ^o and -53.3 (5) ^o, respectively.

The atom N2 is sp²-hybridized, because of the sum of the angles around atom N2 is 359.8 (3) °. The phenyl rings are rotated out of the mean plane of the N1-C1-S1-N2 atoms by 80.1 (2) ° (C2-C7 ring) and 69.96 (19) ° (C8-C13 ring). In addition, the dihedral angle between C2-C7 ring and C8-C13 ring is 72.8 (2) °.

As can be seen from the packing diagram (Fig. 2), intermolecular N-H···S hydrogen bond (Table 1) links the molecules into dimers, which are stacked along the c-axis. The other intermolecular contacts, C-H···O and C-H···S, are also listed in Table 1.

Experimental

The title compound was prepared with a procedure similar to that reported in the literature (Arslan et al., 2003a). A solution of 3-chlorobenzoyl chloride (0.01 mol) in acetone (50 cm³) was added dropwise to a suspension of potassium thiocyanate (0.01 mol) in acetone (30 cm³). The reaction mixture was heated under reflux for 30 min, and then cooled to room temperature. A solution of diphenylamine (0.01 mol) in acetone (10 cm³) was added and the resulting mixture was stirred for 2 h. Hydrochloric acid (0.1 N, 300 cm³) was added to the solution, which was then filtered. The solid product was washed with water and purified by recrystalization from an ethanol:dichloromethane mixture (1:2). Anal. Calcd. for C₂₀H₁₅ClN₂OS: C, 65.5; H, 4.1; N,7.6. Found: C, 65.4; H, 3.9; N, 7.7%.