N-(3-Methyl­phen­yl)-N′-(4-nitro­benzo­yl)thio­urea

Liang Xian

doi:10.1107/S1600536808029425

. 2008 Sep 20;64(Pt 10):o1969. doi: 10.1107/S1600536808029425

N-(3-Methylphenyl)-N′-(4-nitrobenzoyl)thiourea

Liang Xian ^a,^*

PMCID: PMC2959244 PMID: 21201169

Abstract

Two molecules of the title compound, C₁₅H₁₃N₃O₃S, are linked by an intermolecular N—H⋯S hydrogen bond. There is also an intramolecular N—H⋯O hydrogen bond, forming a six-membered ring. The steric restriction of the m-methyl and p-nitro groups, as well as the intramolecular hydrogen bond, are the main factors influencing the molecular conformation.

Related literature

For general background, see: Su et al. (2006 ▶). For related coordination compounds, see: Su et al. (2005 ▶); Xian et al. (2004 ▶). For related structures, see: Su (2005 ▶, 2007 ▶); Yusof et al. (2007 ▶).

Experimental

Crystal data

C₁₅H₁₃N₃O₃S
M _r = 315.34
Monoclinic,
a = 11.381 (10) Å
b = 8.549 (8) Å
c = 15.653 (12) Å
β = 108.012 (16)°
V = 1448 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.24 mm⁻¹
T = 296 (2) K
0.30 × 0.29 × 0.26 mm

Data collection

Bruker APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T _min = 0.609, T _max = 1.000 (expected range = 0.572–0.940)
7125 measured reflections
2692 independent reflections
2072 reflections with I > 2σ(I)
R _int = 0.059

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.141
S = 0.89
2692 reflections
201 parameters
H-atom parameters constrained
Δρ_max = 0.29 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: APEX2 (Bruker, 2001 ▶); cell refinement: APEX2 and SAINT (Bruker, 2001 ▶); 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 global, I. DOI: 10.1107/S1600536808029425/bv2107sup1.cif

e-64-o1969-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808029425/bv2107Isup2.hkl

e-64-o1969-Isup2.hkl^{(132.2KB, 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′⋯S1ⁱ	0.86	2.81	3.665 (4)	179
N4—H4′⋯O3	0.86	1.94	2.643 (3)	138

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Symmetry code: (i) Inline graphic .

Acknowledgments

Financial support of this work by the Foundation of Northwest University for Nationalities is acknowledged.

supplementary crystallographic information

Comment

Thiourea and its derivatives are good ligands for forming coordination compounds with transition metal ions, especially Cu(I). Our previous research showed that coordination compounds of carbonylthiourea derivatives with Cu(I) often adopt a trigonal planar conformation (Xian et al., 2004). In addition, it was found that the reaction of carbonylthiourea derivatives with Cu(I) can also form a metal cluster compound with a complex structure (Su et al., 2005). Apparently, the coordinating ability of carbonylthiorea derivatives is related to their conformation and hydrogen bonds. Herein the structure of N-p-nitrobenzoyl-N'-(m-methylphenyl)thiourea and its FT—IR, ¹H NMR was reported.

As shown in Fig. 1, the title compound adopts a trans-conformation similar to the other structures of thiourea derivatives (Su et al., 2006; Su, 2007), i.e. the conformation in which the thiocarbonyl and carbonyl groups are distributed on opposite sides of the main backbone due to steric restriction. On the other hand, steric restriction and hydrogen bond interactions also result in dimer formation through the "head-tail" junction conformation of the title compound (Fig. 2). The thiocarbonyl group forms an intermolecular hydrogen bond with N—H (-x, -y, -z), and the carbonyl group forms intramolecular hydrogen bond with N—H (x, y, z). Apparently, the carbonyl oxygen atom is "locked" in the hydrogen-bonded six-membered ring structure and thus not readily available for coordination with transition metal ions. There are mainly two molecular planes in the structure, two benzene rings almost are in the same plane with the mean deviation 0.078 (4) Å, another plane is the hydrogen-bonding six-membered ring with the mean deviation 0.055 (4) Å. The angle between two benzene planes is 41.39(0.09)°. The above conformation is similar to that observed in previously reported thiourea structures (Su, 2005; Yusof et al., 2007).

Experimental

All chemicals used for the preparation of the title compound were of reagent grade quality. The infrared spectrum was recorded in the range of 4000–400 cm^-1 on a Nicolet NEXUS 670 F T—IR spectrometer, using KBr pellets. ¹H NMR spectrum was obtained on an INOVA-400 MHz superconducting spectrometer, CDCl₃ was used as the solvent and TMS as internal standard, and the chemical shifts are expressed as delta. Elemental analyses were carried out on a PE-2400 elemental analysis instrument. Melting point determination was performed in YRT-3 melting point instrument (Tianjin) and was uncorrected. The yellow single-crystal was obtained after one week by slow evaporation of the acetone solution of the title compound. N-p-nitrobenzoyl-N'-(m-methylphenyl)thiourea. Color: yellow. Melting Point: 151–153 (°C). Elemental analysis (%) found (calcd.): C, 56.3(61.5); H, 4.11(4.7); N, 10.3(13.2); S, 10.2(10.0). IR (KBr, cm^-1): 3244 (N—H), 1675 (C=O), 1521(C=C), 1336, 1264(C=S), 1151. ¹H NMR(delta, p.p.m.): 2.40 (s, 3H, CH₃); 6.91–9.07 (m, 8H, C₆H₄, C₆H₄); 12.30 (s, 1H, NH).