4-Bromo-N-(diethyl­carbamothio­yl)­benzamide

Gün Binzet; Ulrich Flörke; Nevzat Külcü; Hakan Arslan

doi:10.1107/S1600536809003183

. 2009 Jan 31;65(Pt 2):o427–o428. doi: 10.1107/S1600536809003183

4-Bromo-N-(diethylcarbamothioyl)benzamide

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

PMCID: PMC2968358 PMID: 21582014

Abstract

The synthesis of the title compound, C₁₂H₁₅BrN₂OS, involves the reaction of 4-bromobenzoyl chloride with potassium thiocyanate in dry acetone, followed by condensation of 4-bromobenzoyl isothiocyanate with diethylamine. The carbonyl and thiocarbonyl bond lengths indicate that these correspond to double bonds. The short C—N bond lengths reveal the effects of resonance in this part of the molecule. The conformation of the molecule with respect to the thiocarbonyl and carbonyl units is twisted, with torsion angles of −5.7 (3) and 87.2 (2)°. The N atom of the diethylamine group is sp ²-hybridized: the sum of the angles around the N atom is 359.97 (14)°. The two diethyl groups are twisted in + and − antiperiplanar conformations with angles of −179.89 and 179.92°. In the crystal structure, the molecules form infinite chains via an intermolecular N—H⋯O interaction.

Related literature

For the synthesis, see: Özer et al. (2009 ▶); Arslan, Flörke & Külcü (2003 ▶), and references therein. For general background, see: Koch (2001 ▶); El Aamrani et al. (1998 ▶, 1999 ▶); Arslan et al. (2006 ▶); Arslan, Flörke & Külcü (2007 ▶); Arslan, Flörke, Külcü & Binzet (2007 ▶); Yuan et al. (2001 ▶); Zhang et al. (2004 ▶); Weiqun et al. (2004 ▶). For related compounds, see: Arslan, Külcü & Flörke (2003 ▶); Arslan et al. (2004 ▶); Khawar Rauf et al. (2009a ▶,b ▶); Khawar Rauf, Bolte & Anwar (2009 ▶); Khawar Rauf, Bolte & Rauf (2009 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₂H₁₅BrN₂OS
M _r = 315.23
Monoclinic,
a = 6.9955 (9) Å
b = 18.680 (2) Å
c = 10.0816 (13) Å
β = 95.361 (3)°
V = 1311.7 (3) Å³
Z = 4
Mo Kα radiation
μ = 3.28 mm⁻¹
T = 120 (2) K
0.38 × 0.37 × 0.11 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2002 ▶) T _min = 0.329, T _max = 0.714
10831 measured reflections
3117 independent reflections
2730 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.025
wR(F ²) = 0.064
S = 1.06
3117 reflections
158 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.26 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/S1600536809003183/at2713sup1.cif

e-65-0o427-sup1.cif^{(17KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809003183/at2713Isup2.hkl

e-65-0o427-Isup2.hkl^{(153KB, 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⋯O1ⁱ	0.896 (5)	2.016 (9)	2.882 (2)	162 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work was supported by Mersin University Research Fund [project Nos. BAP-ECZ-F-TBB-(HA) 2004–3 and BAP-FEF-KB-(NK) 2006-3]. This study is part of the PhD thesis of GB.

supplementary crystallographic information

Comment

Transition metal complexes bearing thiourea ligand or its derivatives have been one of the highlights in coordination chemistry, which are used as reactant for extraction of some transition metal ions (Koch, 2001; El Aamrani et al., 1998, 1999). Moreover, the growing interest for thiourea derivative ligands and their metal complexes result from the important role they play in biological systems (Yuan et al., 2001; Zhang et al., 2004; Weiqun et al., 2004).

Recently, our research has focussed on the chemical and physical properties of thiourea derivatives and their metal complexes (Arslan et al., 2006; Arslan, Flörke & Külcü, 2007; Arslan, Flörke, Külcü & Binzet, 2007). In the present work, we report the crystal structure of 4-bromo-N-(diethylcarbamothioyl)benzamide, (I). The molecular structure of the title compound is depicted in Fig. 1.

The typical thiourea carbonyl [C6—O1 = 1.230 (2) Å] and thiocarbonyl (C1—S1 = 1.6638 (18) Å) double bonds as well as shortened C—N bond lengths (C1—N1 (1.435 (2) Å), C1—N2 (1.325 (2) Å) and C6—N1 (1.355 (2) Å)) are observed in the title compound. These bond lengths in the title compound are comparable to those of related structures (Khawar Rauf et al., 2009a,b; Khawar Rauf, Bolte & Anwar, 2009; Khawar Rauf, Bolte & Rauf, 2009; Arslan, Flörke & Külcü, 2003; Arslan et al., 2004). The other bond lengths in (I) show normal values (Allen et al., 1987).

The conformation of the title molecule with respect to the thiocarbonyl and carbonyl moieties is twisted, as reflected by the C1—N1—C6—O1, C6—N1—C1—N2, and C6—N1—C1—S1 torsion angles of -5.7 (3) °, 87.2 (2) ° and -94.57 (18) °, respectively. The dihedral angle between the 4-bromophenyl ring and the plane O1/N1/C7/C6 is 10.10 (3) °, and the dihedral angle between the 4-bromophenyl ring and the plane S1/C1/N1/N2 is 86.98 (3) °. The atom N2 is sp²-hybridized, because of the sum of the angles around atom N2 is 359.97 (14) °. The two diethyl groups are twisted in a + and - antiperiplanar conformation with -179.89 ° and 179.92 °.

Iintermolecular N—H···O (x, -y+1.5, z-0.5) hydrogen bonds (Table 1) link the molecules into endless chains, as shown in Fig. 2.

Experimental

The title compound was prepared with a procedure similar to that reported in the literature (Arslan, Külcü & Flörke, 2003; Özer et al., 2009). A solution of 4-bromobenzoyl 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 diethylamine (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 purifed by recrystalization from an ethanol:dichloromethane mixture (1:2). Analysis calculated for C₁₂H₁₅N₂OSBr: C 45.7, H 4.8, N 8.9%. Found: C 45.7, H 4.9, N 8.7%.