Ethyl 2-[3-(3,5-Dinitrobenzo­yl)thio­ureido]benzoate

Sohail Saeed; Naghmana Rashid; Moazzam H Bhatti; Wing-Tak Wong

doi:10.1107/S1600536811012918

. 2011 Apr 13;67(Pt 5):o1114. doi: 10.1107/S1600536811012918

Ethyl 2-[3-(3,5-Dinitrobenzoyl)thioureido]benzoate

Sohail Saeed ^a,^*, Naghmana Rashid ^a, Moazzam H Bhatti ^a, Wing-Tak Wong ^b

PMCID: PMC3089348 PMID: 21754430

Abstract

In the title compound, C₁₇H₁₄N₄O₇S, the dihedral angle between the two benzene rings is 9.04 (15)°. The centroid–centroid distance of 3.9825 (19) Å between nearly parallel benzene rings of adjacent molecules suggests the existence of π-π stacking. Intermolecular and intra-molecular N—H⋯O hydrogen bonding is present in the structure. The ethoxy group is disordered over two sets of sites with an occupancy ratio of 0.580 (15):0.420 (15). The crystal studied was an inversion twin.

Related literature

For background to the chemistry of thiourea derivatives and their bioloical activity, and a related structure, see: Saeed et al. (2010 ▶).

Experimental

Crystal data

C₁₇H₁₄N₄O₇S
M _r = 418.38
Monoclinic,
a = 11.7264 (19) Å
b = 16.617 (3) Å
c = 9.9630 (16) Å
β = 101.522 (2)°
V = 1902.3 (5) Å³
Z = 4
Mo Kα radiation
μ = 0.22 mm⁻¹
T = 299 K
0.27 × 0.16 × 0.08 mm

Data collection

Bruker SMART 1000 CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2004 ▶) T _min = 0.943, T _max = 0.983
4944 measured reflections
3011 independent reflections
2727 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.037
wR(F ²) = 0.095
S = 1.10
3011 reflections
301 parameters
42 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.24 e Å⁻³
Absolute structure: Flack (1983 ▶), 1340 Friedel pairs
Flack parameter: 0.39 (8)

Data collection: SMART (Bruker, 1998 ▶); cell refinement: SAINT (Bruker, 2006 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEPII (Johnson, 1976 ▶) and Mercury (Macrae et al., 2008 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811012918/xu5177sup1.cif

e-67-o1114-sup1.cif^{(19.3KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811012918/xu5177Isup2.hkl

e-67-o1114-Isup2.hkl^{(147.8KB, 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⋯O2	0.91 (3)	1.95 (3)	2.672 (3)	134 (2)
N1—H1⋯O3	0.91 (3)	2.01 (3)	2.700 (3)	131 (2)
N2—H2⋯O3ⁱ	0.77 (3)	2.32 (3)	3.086 (3)	172 (2)

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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.

supplementary crystallographic information

Comment

The background to this study has been set in our previous work on the structural chemistry of N,N'-disubstituted thiourea (Saeed et al., 2010). Herein, as a continuation of these studies, the structure of the title compound, (I), C₁₇H₁₄N₄O₇S, is described.

The compound is slightly twisted. The nitro groups are 3.9 (5)° and 17 (1)° from the phenyl ring plane of C10—C15. The thiourea plane is making a dihedral angle of 5.3 (2)° with the amido group and makes a dihedral angle of 31.35 (17)° with the phenyl ring plane of C2—C7.

There are inter-molecular N—H···O H-bond interactions which link the molecules to form 1-D chain in the crystal lattice. There are also weak π···π between neighbouring rings in the crystal lattice.

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 dropwise to a suspension of dry potassium thiocyanate (0.01 mol) in acetone (50 ml) and the reaction mixture was refluxed for 50 min. After cooling to room temperature, a solution of ethyl-orthoamino benzoate (0.01 mol) in anhydrous acetone (25 ml) was added dropwise 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 ethyl acetate.