1-Benzoyl-3,3-bis­(2-methyl­prop­yl)thio­urea

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

doi:10.1107/S1600536811004557

. 2011 Feb 12;67(Pt 3):o602. doi: 10.1107/S1600536811004557

1-Benzoyl-3,3-bis(2-methylpropyl)thiourea

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

PMCID: PMC3052116 PMID: 21522360

Abstract

The title compound, C₁₆H₂₄N₂OS, is twisted about the central N(H)—C bond with the C—N—C—S torsion angle being 119.6 (3)°. The carbonyl O and thione S atoms are directed to opposite sides of the molecule, a conformation that allows for the formation of a linear supramolecular chain comprising alternating eight-membered {⋯HNCS}₂ and 14-membered {⋯HCNCNCO}₂ synthons.

Related literature

For the coordinating ability of N,N-dialkyl-N′-benzoylthioureas; see: Binzet et al. (2009 ▶); Gunasekaran et al. (2010 ▶); Sacht et al. (2000 ▶). For the utility of Cd derivatives to serve as synthetic precursors for CdS nanoparticles, see: Bruce et al. (2007 ▶). For their biological activity, see: Arslan et al. (2006 ▶). For related structures, see: Gunasekaran et al. (2010a ▶,b ▶).

Experimental

Crystal data

C₁₆H₂₄N₂OS
M _r = 292.43
Triclinic,
a = 8.9331 (10) Å
b = 10.1023 (9) Å
c = 11.0725 (12) Å
α = 105.776 (9)°
β = 112.734 (10)°
γ = 100.782 (9)°
V = 837.47 (19) Å³
Z = 2
Mo Kα radiation
μ = 0.19 mm⁻¹
T = 295 K
0.35 × 0.30 × 0.25 mm

Data collection

Agilent Supernova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.936, T _max = 0.954
6265 measured reflections
3693 independent reflections
2232 reflections with I > 2σ(I)
R _int = 0.025

Refinement

R[F ² > 2σ(F ²)] = 0.074
wR(F ²) = 0.219
S = 1.04
3693 reflections
181 parameters
12 restraints
H-atom parameters constrained
Δρ_max = 0.86 e Å⁻³
Δρ_min = −0.58 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2010 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶) and DIAMOND (Brandenburg, 2006 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811004557/ez2230sup1.cif

e-67-0o602-sup1.cif^{(18.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811004557/ez2230Isup2.hkl

e-67-0o602-Isup2.hkl^{(181KB, 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	0.88	2.74	3.586 (3)	162
C9—H9a⋯O1ⁱⁱ	0.97	2.49	3.424 (5)	162

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

Acknowledgments

NS thanks the NITT for a Fellowship. The authors thank the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

N,N-Dialkyl-N'-benzoylthioureas are versatile ligands which can coordinate to transition metal centres either as neutral species or in an anionic form. The complexation capacity of thiourea derivatives has been reported in several studies (Binzet et al., 2009; Gunasekaran et al., 2010). Chiral and achiral platinum(II) complexes of these ligands have been used as chemotherapeutic agents (Sacht et al., 2000) while cadmium(II) complexes of N,N-diethyl-N'-benzoylthiourea have been used as single-source precursors for the preparation of CdS nanoparticles (Bruce et al., 2007). In addition, thioureas have been shown to possess anti-tubercular, anti-helmintic, anti-bacterial, insecticidal and rodenticidal properties (Arslan et al., 2006). In continuation of structural studies of these derivatives (Gunasekaran et al., 2010a; Gunasekaran et al., 2010b), the title compound, (I), was investigated.

In (I), Fig. 1, the molecule exhibits a significant twist about the central N(H)–C bond as seen in the value of the C7–N1–C8–S1 torsion angle of 119.6 (3) °. This arrangement causes the carbonyl-O and thione-S atoms to lie on opposite sides of the molecule. Similarly, the carbonyl and N–H groups are directed away from each other. This conformation allows for the formation of N–H···S hydrogen bonds, Table 1, via an eight-membered {···HNCS}₂ ring which has the shape of an elongated chair. These are connected into supramolecular chains along [1 1 1] via C–H···O contacts that close 14-membered {···HCNCNCO}₂ synthons, also adopting the shape of an elongated chair, Table 1 and Fig. 2. Chains are arranged into layers via weak π···π interactions [Cg(C1–C6)···Cg(C1–C6)ⁱ = 3.806 (3) Å for i: 2 - x, 1 - y, 2 - z] and these stack as shown in Fig. 3.

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 min. and then cooled to room temperature. A solution of diisobutyl amine (0.6462 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 for X-ray diffraction were grown at room temperature from an acetonitrile solution of the compound. Yield 72%; M.Pt. 415 K. FT—IR (KBr) ν(N—H) 3268, ν(C═O) 1688, ν(C=S) 1264 cm^-1.