1-Benzoyl-3,3-bis­(propan-2-yl)thio­urea

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

doi:10.1107/S1600536810028862

. 2010 Jul 24;66(Pt 8):o2113. doi: 10.1107/S1600536810028862

1-Benzoyl-3,3-bis(propan-2-yl)thiourea

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

PMCID: PMC3007396 PMID: 21588403

Abstract

Two independent thiourea derivatives comprise the asymmetric unit of the title compound, C₁₄H₂₀N₂OS. The major difference between the molecules relates to a twist in the relative orientation of the benzene rings [torsion angles = 4.5 (2) and −19.9 (2)° for the two independent molecules]. The thiocarbonyl and carbonyl groups lie to opposite sides of the molecule as there are twists about the central N—S bond [torsion angles = 83.90 (15) and 81.77 (15)°]. Supramolecular chains extending parallel to [101] with a stepped topology and mediated by N—H⋯O hydrogen bonding feature in the crystal structure. C—H⋯O and C—H⋯π interactions are also present.

Related literature

For the biological activity of thiourea derivatives, see: Venkatachalam et al. (2004 ▶); Yuan et al. (2001 ▶); Zhou et al. (2004 ▶). For the use of ruthenium(III) complexes of thioureas as catalysts, see: Gunasekaran & Karvembru (2010 ▶). For additional structural analysis, see: Spek (2009 ▶).

Experimental

Crystal data

C₁₄H₂₀N₂OS
M _r = 264.38
Monoclinic,
a = 14.8072 (10) Å
b = 13.5832 (10) Å
c = 14.9168 (11) Å
β = 97.635 (1)°
V = 2973.6 (4) Å³
Z = 8
Mo Kα radiation
μ = 0.21 mm⁻¹
T = 100 K
0.40 × 0.25 × 0.05 mm

Data collection

Bruker SMART APEX diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.921, T _max = 0.990
27965 measured reflections
6833 independent reflections
5254 reflections with I > 2σ(I)
R _int = 0.051

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.097
S = 1.02
6833 reflections
341 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.22 e Å⁻³

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/S1600536810028862/ez2225sup1.cif

e-66-o2113-sup1.cif^{(25.7KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810028862/ez2225Isup2.hkl

e-66-o2113-Isup2.hkl^{(334.4KB, hkl)}

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

Table 1. Hydrogen-bond geometry (Å, °).

Cg is the centroid of the C1–C6 ring.

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N1—H1⋯O2ⁱ	0.85 (1)	2.03 (1)	2.8568 (16)	167 (2)
N3—H3⋯O1	0.85 (1)	1.94 (1)	2.7728 (16)	163 (2)
C6—H6⋯O2ⁱ	0.95	2.40	3.3306 (18)	166
C10—H10c⋯Cgⁱⁱ	0.98	2.63	3.5714 (18)	160
C25—H25b⋯Cgⁱⁱⁱ	0.98	2.70	3.5717 (18)	149

Open in a new tab

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

Acknowledgments

NG thanks NITT for a Fellowship.

supplementary crystallographic information

Comment

Thiourea and its derivatives 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). N-[Di(alkyl/aryl)carbamothioyl]benzamide derivatives provide immense opportunities for altering electronic and steric effects in its metal complexes. This might help in designing effective catalysts. Ruthenium(III) complexes containing these ligands have recently been used as catalysts for oxidation of alcohols to carbonyl compounds (Gunasekaran et al., 2010). The structure of the title thiourea derivative, (I), was investigated to provide reference data for subsequent studies.

Two independent molecules comprise the asymmetric unit of (I). The first independent molecule, Fig. 1, is virtually super-imposable upon the second, Fig. 2, with the major difference between them being a twist in the benzene rings, Fig. 3. This is quantified by the C2–C1–C7–O1 and C16–C15–C21–O2 torsion angles of 4.5 (2) and -19.9 (2) °, respectively. This is also reflected in the r.m.s. deviation for bond distances and angles of 0.0035 Å and 0.903 °, respectively (Spek, 2009). The molecules are twisted about the central thiourea bond as seen in the C7—N1—C8—S1 and C21—N3—C22—S2 torsion angles of 83.90 (15) and 81.77 (15) °, respectively, indicating that the thiocarbonyl and carbonyl groups lie to opposite sides of the molecule.

The most notable feature in the crystal packing is the formation of supramolecular chains mediated by N–H···O hydrogen bonding, Table 1; chains are reinforced by C–H···O contacts involving the O2 atom, Table 1. The chains comprise alternating pairs of molecules of opposite orientation so that the topology is stepped. Chains aggregate into layers in the ac plane with the primary interactions between them along the b axis being of the type C–H···π, Fig. 5 and Table 1.

Experimental

A solution of benzoyl chloride (0.70285 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 diisopropyl amine (0.5059 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 ethyl acetate solution by the diffusion of diethyl ether vapour. Yield 78%; M. Pt. 383 K; FT—IR (KBr) ν(N—H) 3249, ν(C═O) 1651, ν(C═ S) 1279 cm^-1.