1-(4-Nitro­benzo­yl)-3-(4-nitro­phen­yl)­thio­urea acetone hemisolvate

Liang Xian; Lujuan Cui; Ming Cheng

doi:10.1107/S160053680803359X

. 2008 Oct 18;64(Pt 11):o2138. doi: 10.1107/S160053680803359X

1-(4-Nitrobenzoyl)-3-(4-nitrophenyl)thiourea acetone hemisolvate

Liang Xian ^a,^*, Lujuan Cui ^a, Ming Cheng ^a

PMCID: PMC2959497 PMID: 21580998

Abstract

In the title compound, C₁₄H₁₀N₄O₅S·0.5C₃H₆O, the nitrobenzoyl and nitrophenyl groups have trans and cis configurations, respectively, with respect to the thiourea S atom. The molecular conformation is stabilized by intramolecular N—H⋯O and C—H⋯S hydrogen bonds. The acetone solvent molecule possesses a crystallographically imposed twofold axis. In the crystal packing, thiourea molecules are linked by intermolecular C—H⋯O hydrogen-bond interactions to form chains running parallel to the c axis. The chains are further bridged via N—H⋯O and C—H⋯O hydrogen bonds involving the acetone molecules.

Related literature

For general background on the chemistry of thiourea derivatives, see: Choi et al. (2008 ▶); Jones et al. (2008 ▶); Kushwaha et al. (2008 ▶); Su et al. (2006 ▶). For related structures, see: Su (2005 ▶, 2007 ▶). For graph-set notation, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₄H₁₀N₄O₅S·0.5C₃H₆O
M _r = 375.36
Monoclinic,
a = 30.828 (14) Å
b = 7.534 (3) Å
c = 15.224 (7) Å
β = 107.262 (12)°
V = 3377 (3) Å³
Z = 8
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 296 (2) K
0.34 × 0.31 × 0.27 mm

Data collection

Bruker SMART CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1996 ▶) T _min = 0.924, T _max = 0.941
9659 measured reflections
3926 independent reflections
2804 reflections with I > 2σ(I)
R _int = 0.023

Refinement

R[F ² > 2σ(F ²)] = 0.043
wR(F ²) = 0.133
S = 1.05
3926 reflections
245 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 1998 ▶); 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/S160053680803359X/rz2253sup1.cif

e-64-o2138-sup1.cif^{(19.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S160053680803359X/rz2253Isup2.hkl

e-64-o2138-Isup2.hkl^{(192.5KB, 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
C1—H1⋯S1	0.93	2.79	3.235 (2)	111
N2—H2A⋯O3	0.90 (3)	1.88 (3)	2.659 (3)	144 (2)
C2—H2⋯O4ⁱ	0.93	2.48	3.394 (3)	167
C12—H12⋯O5ⁱⁱ	0.93	2.54	3.318 (3)	141
N3—H3A⋯O6	0.86 (2)	2.442 (19)	3.300 (2)	175 (2)
C13—H13⋯O6	0.93	2.59	3.207 (3)	124
C14—H14B⋯O5ⁱⁱⁱ	0.96	2.56	3.446 (3)	154
C14—H14C⋯O4^iv	0.96	2.52	3.476 (3)	175

Open in a new tab

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

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 broadly applied in anion recognition, nonlinear optics and catalysis, and display also high bioactivity and good coordination ability (Choi et al., 2008; Kushwaha et al., 2008; Jones et al. 2008; Su et al., 2006). As part of our research on thiourea coordination chemistry, we are interested in the study of the influence of noncovalent interactions, especially hydrogen bonds and π-π stacking interactions, on the coordination modes of benzoylthiourea with transition metal ions. In the present paper, the crystal structure of the title compound is reported.

In the molecule of the title compound (Fig. 1), the nitrobenzoyl and nitrophenyl groups have trans and cis configurations, respectively, with respect of the thiourea S atom. The dihedral angle formed by the two aromatic rings is 7.68 (6)°. The molecular conformation is stabilized by intramolecular N—H···O and C—H···S hydrogen bonds (Table 1) forming six-membered rings of graph set S(6) (Bernstein et al., 1995). This conformation is similar to that reported for N-(4-chlorophenyl)-N'-(4-nitrobenzoyl)urea (Su, 2005) and for N-(p-nitrobenzoyl)-N'-(p-chlorophenyl)thiourea (Su, 2007). The acetone solvent molecule has a crystallographically imposed twofold symmetry. In the crystal packing (Fig. 2), thiourea molecules are linked into chains running parallel to the c axis by intermolecular C—H···O hydrogen bonds (Table 1). These chains are further bridged via N—H···O and C—H···O hydrogen bonds (Table 1) involving the acetone molecules.

Experimental

All reagents and organic solvents were of analytical reagent grade and commercially available. p-Nitrobenzoyl chloride (1.86 g) was treated with ammonium thiocyanate (1.20 g) in CH₂Cl₂ under solid-liquid phase transfer catalysis conditions, using 3% polyethylene glycol-400 as catalyst, to give the corresponding benzoyl isothiocyanate, which was reacted with p-nitroaniline (1.38 g) to give the title compound. The solid was separated from the liquid phase by filtration, washed with CH₂Cl₂ and then dried in air. Yellow single crystals suitable for X-ray analysis were obtained after one week by slow evaporation of an acetone solution. 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 superconduction spectrometer, DMSO-_d6 was used as 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. Melting Point: 201–204°C. Elemental analysis (%) found (calcd.): C, 50.25(49.6); H, 3.55(3.47); N, 11.30(14.93); S, 8.50(8.53). IR (KBr, cm^-1): 3385 (N—H), 3064, 1680 (C=O), 1571(C=C), 1318, 1259(C=S), 1137, 1106. ¹H NMR(delta, p.p.m.): 2.50 (s, 6H, 2CH₃); 8.07–8.38 (m, 8H, 2C₆H₄); 12.15 (s, 1H, NH); 12.61 (s, 1H, NH).