3-Benzoyl-1,1-dibenzyl­thio­urea

N Gunasekaran; R Karvembu; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536810036226

. 2010 Sep 18;66(Pt 10):o2572–o2573. doi: 10.1107/S1600536810036226

3-Benzoyl-1,1-dibenzylthiourea

N Gunasekaran ^a, R Karvembu ^a,^‡, Seik Weng Ng ^b, Edward R T Tiekink ^b,^*

PMCID: PMC2983284 PMID: 21587556

Abstract

Two independent thiourea molecules comprise the asymmetric unit of the title compound, C₂₂H₂₀N₂OS. The central N–C(=S)N(H)C(=O) atoms in each molecule are virtually superimposable and each is twisted [C—N—C—S torsion angles = 121.3 (3) and −62.3 (4)°]. The molecules differ only in terms of the relative orientations of the benzyl benzene rings [major difference between the C—N—C—C torsion angles of −146.6 (3) and −132.9 (3)°]. The presence of N—H⋯S hydrogen bonding leads to the formation of supramolecular chains along the a axis. These are consolidated in the crystal packing by C—H⋯O interactions. The crystal was found to be a combined non-merohedral and racemic twin (twin law Inline graphic 00/00/001), with the fractional contribution of the minor components being approximately 9 and 28%.

Related literature

For our studies of thiourea and its derivatives, see: Gunasekaran et al. (2010 ▶). For the biological activity of thiourea derivatives, see: Venkatachalam et al. (2004 ▶); Yuan et al. (2001 ▶); Zhou et al. (2004 ▶). For additional geometric analysis, see: Spek (2009 ▶).

Experimental

Crystal data

C₂₂H₂₀N₂OS
M _r = 360.46
Monoclinic,
a = 7.7338 (5) Å
b = 24.3478 (16) Å
c = 9.8593 (6) Å
β = 90.074 (1)°
V = 1856.5 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 100 K
0.30 × 0.20 × 0.10 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.946, T _max = 0.982
17536 measured reflections
8469 independent reflections
7807 reflections with I > 2σ(I)
R _int = 0.055

Refinement

R[F ² > 2σ(F ²)] = 0.058
wR(F ²) = 0.157
S = 1.03
8469 reflections
470 parameters
1 restraint
H-atom parameters constrained
Δρ_max = 1.27 e Å⁻³
Δρ_min = −0.36 e Å⁻³
Absolute structure: Flack (1983 ▶), 4101 Friedel pairs
Flack parameter: 0.25 (8)

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶), DIAMOND (Brandenburg, 2006 ▶) and Qmol (Gans & Shalloway, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810036226/lh5120sup1.cif

e-66-o2572-sup1.cif^{(28.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810036226/lh5120Isup2.hkl

e-66-o2572-Isup2.hkl^{(414.3KB, 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⋯S2	0.86	2.54	3.334 (3)	154
N4—H4⋯S1ⁱ	0.86	2.54	3.334 (3)	154
C13—H13⋯O2ⁱⁱ	0.95	2.57	3.193 (5)	124
C14—H14⋯O2ⁱⁱ	0.95	2.60	3.207 (5)	122
C25—H25⋯O1ⁱⁱⁱ	0.95	2.55	3.228 (4)	129

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

Acknowledgments

NG thanks the NITT for a Fellowship. The authors also thank the University of Malaya for support of the crystallographic facility.

supplementary crystallographic information

Comment

The title compound, (I), was investigated in continuation of studies (Gunasekaran et al., 2010) of thiourea and its derivatives, which are useful as anti-tumour, anti-fungal, anti-bacterial, insecticidal, herbicidal, pesticidal agents, and plant-growth regulators (Venkatachalam et al., 2004; Yuan et al., 2001; Zhou et al., 2004).

Two independent molecules comprise the asymmetric unit of (I). The central N–C(═S)N(H)C(═O) atoms of the first independent molecule, Fig. 1, are virtually super-imposable upon those of the second, Fig. 2. The C7–N2–C8–S1 and C29–N4 –C30–N3 torsion angles of 121.3 (3) and -62.3 (4) °, respectively, indicate significant twists in the central part of each molecule. The major differences between the molecules relate to the orientations of the benzene rings as indicated in Fig. 3. The major conformational difference is quantified in the C8–N1–C9–C10 and C30–N3–C38–C39 torsion angles -146.6 (3) and -132.9 (3) °, respectively. The r.m.s. deviations for bond distances and angles are 0.0105 Å and 0.651 °, respectively (Spek, 2009).

The most notable feature in the crystal packing is the formation of supramolecular chains along the a axis mediated by N–H···S hydrogen bonding, Fig. 4 and Table 1. The chains pack in the ac plane and stack along the b axis with the primary connections along this axis being of the type C–H···O, Fig. 5 and Table 1.

Experimental

A solution of benzoyl chloride (0.7029 g, 5 mmol) in acetone (50 ml) was added drop wise to a suspension of potassium thiocyanate (0.4859 g, 5 mmol) in anhydrous acetone (50 ml). The reaction mixture was heated under reflux for 45 minutes and then cooled to room temperature. A solution of dibenzyl amine (0.9864 g, 5 mmol) in acetone (30 ml) was added and the resulting mixture was stirred for 2 h. Hydrochloric acid (0.1 N, 300 ml) was added and the resulting white solid was filtered, washed with water and dried in vacuo. Single crystals were grown at room temperature from its ethyl acetate solution by the diffusion of diethyl ether vapour. Yield 78%; M. Pt. 403 K; FT—IR (KBr) ν(N–H) 3239, ν(C═O) 1690, ν(C═S) 1314 cm^-1.