1-(2,6-Dichloro­benzo­yl)-3-(3-nitro­phen­yl)thio­urea dimethyl­formamide solvate

Min Li; Dongxiao Hou

doi:10.1107/S1600536809055056

. 2010 Jan 9;66(Pt 2):o280. doi: 10.1107/S1600536809055056

1-(2,6-Dichlorobenzoyl)-3-(3-nitrophenyl)thiourea dimethylformamide solvate

Min Li ^a,^*, Dongxiao Hou ^b

PMCID: PMC2979807 PMID: 21579716

Abstract

In the title compound, C₁₄H₉Cl₂N₃O₃S·C₃H₇NO, the two aromatic rings enclose a dihedral angle of 32.93 (12)°. The thiourea molecule exists in its thione form in the solid state with typical C=S and C—N bond lengths. In the crystal, N—H⋯O hydrogen bonds exist between the thiourea and carbonyl groups on the same and neighboring molecules. In addition, each dimethylformamide solvate molecule forms a hydrogen bond to one N atom of the thiourea group.

Related literature

For general background to the use of thiourea and urea derivatives in the development of agrochemicals and pharmacological agents, see: Darlington et al. (1996 ▶); Dowding & Leeds (1971 ▶); Sasse et al. (1969 ▶). For bond lengths in other other substituted thioureas, see: Khawar Rauf et al. (2006a ▶,b ▶,c ▶, 2007 ▶, 2009 ▶). For previously reported C=S distances, see: Bailey et al. (1997 ▶).

Experimental

Crystal data

C₁₄H₉Cl₂N₃O₃S·C₃H₇NO
M _r = 443.30
Triclinic,
a = 8.507 (5) Å
b = 10.240 (5) Å
c = 12.414 (8) Å
α = 70.40 (4)°
β = 81.74 (5)°
γ = 87.98 (4)°
V = 1008 (1) Å³
Z = 2
Mo Kα radiation
μ = 0.46 mm⁻¹
T = 293 K
0.30 × 0.20 × 0.20 mm

Data collection

Bruker SMART APEX CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 1997 ▶) T _min = 0.875, T _max = 0.914
4551 measured reflections
3413 independent reflections
2691 reflections with I > 2σ(I)
R _int = 0.021

Refinement

R[F ² > 2σ(F ²)] = 0.046
wR(F ²) = 0.139
S = 1.11
3413 reflections
256 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Data collection: SMART (Siemens, 1996 ▶); cell refinement: SAINT (Siemens, 1996 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809055056/ez2196sup1.cif

e-66-0o280-sup1.cif^{(19.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809055056/ez2196Isup2.hkl

e-66-0o280-Isup2.hkl^{(167.4KB, 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	0.86	2.47	3.182 (3)	141
N2—H2⋯O1	0.86	1.99	2.675 (3)	136
N1—H1⋯O4ⁱⁱ	0.86	1.96	2.787 (3)	161

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

supplementary crystallographic information

Comment

Earlier studies have shown that thiourea and urea derivatives have played an important role in developing agrochemicals and pharmacological agents (Dowding & Leeds, 1971; Sasse et al., 1969; Darlington et al., 1996). As part of our interest in N,N'-disubstituted thioureas, we now report the crystal structure of the title compound (I).

The N—C bonds in (I), see Fig. 1, differ significantly from one another but are short in comparison with the typical value for an N—C single bond (1.479 Å). Owing to the introduction of the C=O electron-acceptor group the adjacent C-S bond length [1.652 (2)Å ] is shorter than previously reported C=S distances (1.710 (7)Å) (Bailey, et al., 1997). These distances are similar to those usually found in other substituted thioureas (Khawar Rauf et al., 2006a, 2006b, 2006c, 2007, 2009). The dihedral angle between the aromatic rings is 32.93 (12)°, and the corresponding angles with the thiourea plane are 83.52 (7)° for the C2–C7 ring and 50.61 (7)° for the C9–C14 ring.The thiocarbonyl and carbonyl groups are almost coplanar.

Inter- and intramolecular N—H···O hydrogen bonds exist between the thiourea N—H-atoms and carbonyl-O atoms. In addition, each dimethylformamide solvate molecule also has a hydrogen bond to the N of the thiourea groups (2.787 (3) Å: Table 1, Fig. 2).

Experimental

Freshly prepared 2,6-dichlorobenzoylisothiocyanate (2.32 g, 10 mmol) was added to dimethylformamide (30 ml) and stirred for 2 minutes. Afterwards neat 3-nitroaniline (1.38 g, 10 mmol) was added and the resulting mixture was stirred for 1 h.The reaction mixture was then poured into an ice-water mixture and stirred well. The solid product was separated and washed with deionized water and purified by recrystallization from methanol/CH₂Cl₂ (1:1 v/v) to give fine crystals of the title compound (I), with an overall yield of 85%.