3-Cyclo­hexyl-1-(3,5-dinitro­benzo­yl)thio­urea

Sohail Saeed; Naghmana Rashid; Muhammad Sher; Seik Weng Ng; Edward R T Tiekink

doi:10.1107/S1600536811013377

. 2011 Apr 16;67(Pt 5):o1148. doi: 10.1107/S1600536811013377

3-Cyclohexyl-1-(3,5-dinitrobenzoyl)thiourea

Sohail Saeed ^a,^‡, Naghmana Rashid ^a, Muhammad Sher ^a, Seik Weng Ng ^b, Edward R T Tiekink ^b,^*

PMCID: PMC3089179 PMID: 21754456

Abstract

The structure of the title thiourea derivative, C₁₄H₁₆N₄O₅S, features an almost planar central C₂N₂OS fragment (r.m.s. deviation = 0.005 Å), an arrangement stabilized by an intramolecular N—H⋯O hydrogen bond. The terminal rings are twisted out of this plane, the dihedral angle formed with the benzene ring being 33.22 (10)°. The cyclohexyl ring is disordered, with two orientations (50:50) being resolved. The mean plane passing through the atoms of each disordered component forms dihedral angles of 65.7 (2) and 82.4 (3)° with the central plane. Centrosymmetric dimers mediated by an eight-membered {⋯HNC=S}₂ synthon occur in the crystal.

Related literature

For the biological activity of thiourea derivatives, see: Venkatachalam et al. (2004 ▶); Saeed et al. (2011 ▶). For related thiourea structures, see: Gunasekaran et al. (2010 ▶); Saeed et al. (2010 ▶); Dzulkifli et al. (2011 ▶).

Experimental

Crystal data

C₁₄H₁₆N₄O₅S
M _r = 352.37
Monoclinic,
a = 12.3404 (7) Å
b = 9.0506 (5) Å
c = 14.6534 (6) Å
β = 90.385 (5)°
V = 1636.57 (15) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 295 K
0.20 × 0.15 × 0.10 mm

Data collection

Agilent Technologies SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.955, T _max = 0.977
7954 measured reflections
3649 independent reflections
1948 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.061
wR(F ²) = 0.211
S = 1.01
3649 reflections
271 parameters
25 restraints
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.28 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/S1600536811013377/hb5839sup1.cif

e-67-o1148-sup1.cif^{(21.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013377/hb5839Isup2.hkl

e-67-o1148-Isup2.hkl^{(178.9KB, 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⋯O1	0.88	1.89	2.639 (4)	142
N1—H1′⋯O1	0.88	1.99	2.639 (4)	130
N2—H2⋯S1ⁱ	0.88	2.65	3.449 (3)	152

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors are grateful to Allama Iqbal Open University, Islamabad, Pakistan, for the allocation of research and analytical laboratory facilities. The authors also thank the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

Continuing structural studies (Gunasekaran et al. 2010; Saeed et al. 2010; Dzulkifli et al., 2011) of thiourea derivatives are motivated by their biological potential (Venkatachalam et al., 2004; Saeed et al., 2011) and led to the investigation of the title compound, (I).

The molecular structure of (I), Fig. 1, is highly twisted with dihedral angles formed between the central chromophore (r.m.s. = 0.0054 Å for C7,C8,N1,N2,O1 & S1) and the benzene ring being 33.22 (10) °. Two orientations of equal weight were found for the cyclohexyl ring, each with a chair conformation, and these make angles of 65.74 (24) and 82.42 (30) °, respectively, with the central plane. The N—H atoms are anti as are the S and O atoms. As a consequence, the N1—H atom forms an intramolecular hydrogen bond with the carbonyl-O1 atom to close a pseudo six-membered ring, Table 1; there are two values cited owing to the disorder in the molecule. The nitro groups are effectively co-planar with the benzene ring to which they are bonded as seen in the values of the O2—N3—C11—C10 and O4—N4—C13—C12 torsion angles of 1.2 (5) and -7.0 (5) °, respectively.

The most prominent feature of the crystal packing is the formation of centrosymmetric eight-membered {···HNC═S}₂ synthon leading to dimeric aggregates, Fig. 2 and Table 1.

Experimental

A solution of 3,5-dinitrobenzoyl chloride (0.01 mol) in anhydrous acetone (75 ml) and 3% tetrabutylammonium bromide (TBAB), as a phase-transfer catalyst (PTC), in anhydrous acetone was added drop-wise to a suspension of dry potassium thiocyanate (0.01 mol) in acetone (50 ml). The reaction mixture was refluxed for 50 min. After cooling to room temperature, a solution of cyclohexylamine (0.01 mol) in anhydrous acetone (25 ml) was added drop-wise and the resulting mixture refluxed for 3 h. Hydrochloric acid (0.1 N, 300 ml) was added and the solution was filtered. The solid product was washed with water and purified by re-crystallization from ethanol; Yield: 1.50 g (88%) and M.pt. 409 K. IR (KBr, cm^-1): 3215 ν(NH), 1673 (C=O), 1527 (benzene ring), 1138 ν(C═S). Anal. Calcd. for C₁₄H₁₆N₄O₅S: C, 47.72; H, 4.58; N, 15.90; S, 9.10%. Found: C, 47.51; H, 4.75; N, 15.88; S, 9.11%.