1-(3,5-Dinitro­benzo­yl)-3,3-dipropyl­thio­urea

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

doi:10.1107/S1600536811013638

. 2011 Apr 16;67(Pt 5):o1162. doi: 10.1107/S1600536811013638

1-(3,5-Dinitrobenzoyl)-3,3-dipropylthiourea

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

PMCID: PMC3089134 PMID: 21754469

Abstract

The title thiourea derivative, C₁₄H₁₈N₄O₅S, features two substantial twists between its component fragments: the dihedral angle between the SN₂C (thiourea) and ONC₂ (amide) residues is 48.89 (7)° and that between the benzene ring and the amide residue is 30.27 (7)°. In the crystal, molecules are linked by bifurcated N—H⋯(O,S) hydrogen bonds, generating [001] supramolecular chains.

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

C₁₄H₁₈N₄O₅S
M _r = 354.38
Monoclinic,
a = 7.9406 (4) Å
b = 21.2839 (10) Å
c = 9.5967 (4) Å
β = 94.379 (4)°
V = 1617.17 (13) Å³
Z = 4
Mo Kα radiation
μ = 0.23 mm⁻¹
T = 295 K
0.30 × 0.20 × 0.10 mm

Data collection

Agilent SuperNova Dual diffractometer with an Atlas detector
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2010 ▶) T _min = 0.933, T _max = 0.977
8055 measured reflections
3614 independent reflections
2878 reflections with I > 2σ(I)
R _int = 0.027

Refinement

R[F ² > 2σ(F ²)] = 0.055
wR(F ²) = 0.154
S = 1.02
3614 reflections
221 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 1.04 e Å⁻³
Δρ_min = −0.46 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/S1600536811013638/hb5845sup1.cif

e-67-o1162-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013638/hb5845Isup2.hkl

e-67-o1162-Isup2.hkl^{(177.2KB, 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⋯O1ⁱ	0.87 (1)	2.53 (2)	3.264 (3)	142 (2)
N2—H2⋯S1ⁱ	0.87 (1)	2.69 (2)	3.436 (2)	144 (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. The authors also thank the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

The biological potential of thiourea derivatives (Venkatachalam et al., 2004; Saeed et al., 2011) motivates structural studies of these compounds (Gunasekaran et al. 2010; Saeed et al. 2010; Dzulkifli et al., 2011). Herein, the crystal and molecular structure of the title thiourea derivative, (I), is described.

The molecular structure of (I), Fig. 1, shows a significant twist around the central atoms as seen in the value of the dihedral angle formed between the least-squares planes through the S1,N1,N2,C7 (thiourea) and O1,N2,C8,C9 (amide) atoms of 48.89 (7) °. Further, the benzene ring is twisted out of the plane of the carbonyl residue as indicated by the O1—C8—C9—C10 torsion angle of 147.1 (2) °. With respect to the S1,N1,N2,C7 plane, the n-propyl groups lie to either side. Whereas the O2-nitro group is co-planar with the benzene ring to which it is bonded, the O2—N3—C11—C10 torsion angle = -4.2 (3) °, the O4-nitro group is slightly twisted out of the plane as seen in the value of the O4—N4—C13—C12 torsion angle of -9.3 (3) °.

The crystal packing is dominated by N—H···O,S hydrogen bonds as the N1—H H atoms is bifurcated, Table 1. These result in the formation of six-membered {···H···OCNCS} synthons and linear supramolecular chains along the c direction, Fig. 2.

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) and the reaction mixture was refluxed for 50 min. After cooling to room temperature, a solution of dipropyl amine (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 ethyl acetate to yield light-yellow prisms of (I). Yield: 1.29 g (82%); M.pt. 407–408 K. IR (KBr, cm^-1): 3173 ν(NH), 1690 ν(C═O), 1536 ν(benzene ring), 1180 ν(C═S). Anal. Calcd. for C₁₄H₁₈N₄O₅S: C, 47.45; H, 5.12; N, 15.81; S, 9.05%. Found: C, 47.53; H, 5.17; N, 15.75; S, 9.03%.