4-Bromo-N-(di-n-propyl­carbamothioyl)­benzamide

Gün Binzet; Ulrich Flörke; Nevzat Külcü; Hakan Arslan

doi:10.1107/S1600536809003511

. 2009 Feb 4;65(Pt 3):o452–o453. doi: 10.1107/S1600536809003511

4-Bromo-N-(di-n-propylcarbamothioyl)benzamide

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

PMCID: PMC2968555 PMID: 21582125

Abstract

The synthesis of the title compound, C₁₄H₁₉BrN₂OS, involves the reaction of 4-bromobenzoyl chloride with potassium thiocyanate in acetone followed by condensation of the resulting 4-bromobenzoyl isothiocyanate with di-n-propylamine. Typical thiourea carbonyl and thiocarbonyl double bonds, as well as shortened C—N bonds, are observed in the title compound. The short C—N bond lengths in the centre of the molecule reveal the effects of resonance in this part of the molecule. The asymmetric unit of the title compound contains two crystallographically independent molecules, A and B. There is very little difference between the bond lengths and angles of these molecules. In molecule B, one di-n-propyl group is twisted in a −antiperiplanar conformation with C—C—C—H = −179.1 (3)° and the other adopts a −synclinal conformation with C—C—C—H = −56.7 (4)°; in molecule A the two di-n-propyl groups are twisted in + and −antiperiplanar conformations, with C—C—C—H = −179.9 (3) and 178.2 (3)°, respectively. In the crystal, the molecules are linked into dimeric pairs via pairs of N—H⋯S hydrogen bonds.

Related literature

For synthesis, see: Özer et al. (2009 ▶); Mansuroğlu et al. (2008 ▶); Uğur et al. (2006 ▶); Arslan et al. (2003b ▶, 2006 ▶), and references therein. For general background, see: Koch (2001 ▶); El Aamrani et al. (1998 ▶, 1999 ▶); Arslan et al. (2006 ▶, 2007a ▶,b ▶). For related compounds, see: Khawar Rauf et al. (2009a ▶,b ▶,c ▶,d ▶); Arslan et al. (2003a ▶, 2004 ▶). For bond-length data, see: Allen et al. (1987 ▶).

Experimental

Crystal data

C₁₄H₁₉BrN₂OS
M _r = 343.28
Monoclinic,
a = 21.104 (3) Å
b = 9.6940 (12) Å
c = 16.208 (2) Å
β = 108.956 (3)°
V = 3135.9 (7) Å³
Z = 8
Mo Kα radiation
μ = 2.75 mm⁻¹
T = 120 (2) K
0.48 × 0.18 × 0.17 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.352, T _max = 0.652
27091 measured reflections
7470 independent reflections
4686 reflections with I > 2σ(I)
R _int = 0.074

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.094
S = 0.97
7470 reflections
340 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.70 e Å⁻³
Δρ_min = −0.71 e Å⁻³

Data collection: SMART (Bruker, 2002 ▶); cell refinement: SAINT (Bruker, 2002 ▶); 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 I, global. DOI: 10.1107/S1600536809003511/at2717sup1.cif

e-65-0o452-sup1.cif^{(26.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809003511/at2717Isup2.hkl

e-65-0o452-Isup2.hkl^{(365.5KB, 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
N11—H1⋯S2	0.896 (15)	2.600 (19)	3.460 (3)	161 (3)
N21—H2⋯S1	0.899 (14)	2.566 (17)	3.452 (3)	169 (2)

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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

Thiourea derivative ligands and their metal complexes have been one of the highlights in coordination chemistry. The thiourea ligands which contain carbonyl and thiocarbonyl groups are used as reactant for extraction of some transition metal ions (Koch, 2001; El Aamrani et al., 1998, 1999). The structures of thiourea derivatives and its metal complexes have been determined during the last years. The title compound derivative acts as a bidentate ligand coordinating through the S atom and the O atom.

The similar structures of these derivatives palladium, nickel, cobalt, and copper complexes and ligands have been determined in previous studies (Özer et al., 2009; Arslan et al., 2003b, 2006; Mansuroğlu et al., 2008; Uğur et al., 2006). The title compound, 4-bromo-N-(di-n-propylcarbamothioyl)benzamide, (I), is another example of our newly synthesized thiourea derivatives that contains both aryl and alkyl groups.

The molecular structure of the title compound is depicted in Fig. 1. The asymmetric unit of the title compound contains two crystallographically independent molecules A (atom numbering 1xx) and B (2xx). There is very little difference between the bond lengths and angles of these molecules.

The typical thiourea carbonyl and thiocarbonyl double bonds as well as shortened C—N bond lengths are observed in the title compound. These bond lengths in the title compound are comparable to those of related structures; 1-(4-chlorobenzoyl)-3-(2,4,6-trichlorophenyl)thiourea (Khawar Rauf et al., 2009b), 1-(3-chlorophenyl)-3-(2,6-dichlorobenzoyl)thiourea (Khawar Rauf et al., 2009d), 1-(3-chlorobenzoyl)-3-(2,3-dimethylphenyl)thiourea (Khawar Rauf et al., 2009c), 1-(2,6-dichlorobenzoyl)-3-(2,3,5,6-tetrachlorophenyl)thiourea (Khawar Rauf et al., 2009a), N'-(4-chlorobenzoyl)-N,N-diphenylthiourea (Arslan et al., 2003a), 1-(2-chloro-benzoyl)-3-p-tolyl-thiourea (Arslan et al., 2004), N,N-dimethyl-N-(2-chlorobenzoyl)thiourea (Arslan et al., 2006), o-ethylbenzoylthiocarbamate (Arslan et al., 2007a), 2-chloro-N-(diethylcarbamothioyl)benzamide (Arslan et al., 2007b). 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 C101—N11—C108—O1, C108—N11—C101—S1, C108—N11—C101—N12, C201—N21—C208—O2, C208—N21—C201—S2, and C208—N21—C201—N22 torsion angles of 11.9 (5), 110.7 (3), -69.6 (4), -13.6 (5), -109.6 (3), and 70.5 (4)°, respectively. In addition, the difference in the torsion angles can be attributed to the different conformations of the two independent molecules.

The two di-n-propyl groups in independent molecules A (atom numbering 1xx) are twisted in a + and - antiperiplanar conformation with -179.9 (3)° and 178.2 (3)°. In the independent molecule B (atom numbering 2xx), one di-n-propyl group is twisted in a - antiperiplanar conformation with -179.1 (3)° and the other di-n-propyl group adopts a - synclinal conformation with -56.7 (4)°.

The phenyl rings and central thiourea S1—N11—N12—C101 [largest dev. 0.002 (3) Å for C101] and S2—N21—N22—C201 [largest dev. -0.001 (3) Å for C201] fragments are each essentially planar. The dihedral angle between the 4-bromophenyl ring and the plane S1/N11/N12/C101 is 84.88 (15)°, and the dihedral angle between the 4-bromophenyl ring and the plane S2/N21/N22/C201 is 82.53 (16)°.

The molecules of title compound are linked by paired N—H···S hydrogen bonds into centrosymmetric dimers. Details of the symmetry codes and hydrogen bonding are given in Table 1 and Fig. 2.

Experimental

The title compound was prepared with a procedure similar to that reported in the literature (Arslan et al., 2003b; Özer et al., 2009). A solution of 4-bromobenzoyl chloride (0.01 mol) in acetone (50 ml) was added dropwise to a suspension of potassium thiocyanate (0.01 mol) in acetone (30 ml) (Fig. 3). The reaction mixture was heated under reflux for 30 min, and then cooled to room temperature. A solution of di-n-propylamine (0.01 mol) in acetone (10 ml) was added and the resulting mixture was stirred for 2 h. Hydrochloric acid (0.1 N, 300 ml) was added to the solution, which was then filtered. The solid product was washed with water and purifed by recrystallization from an ethanol–dichloromethane mixture (1:2). Anal. Calcd. for C₁₄H₁₉N₂OSBr: C, 48.9; H, 5.6; N, 8.2. Found: C, 48.7; H, 5.4; N, 8.4%.