3-Acetyl-1-(2,3-dichloro­phen­yl)thio­urea

B Thimme Gowda; Sabine Foro; Sharatha Kumar

doi:10.1107/S1600536812030176

. 2012 Jul 7;68(Pt 8):o2353. doi: 10.1107/S1600536812030176

3-Acetyl-1-(2,3-dichlorophenyl)thiourea

B Thimme Gowda ^a,^*, Sabine Foro ^b, Sharatha Kumar ^a

PMCID: PMC3414287 PMID: 22904820

Abstract

In the crystal structure of the title compound, C₉H₈Cl₂N₂OS, there are two molecules in the asymmetric unit which are connected by a pair of N—H⋯S hydrogen bonds. An intramolecular N—H⋯O hydrogen bond stabilizes the molecular conformation of each molecule.

Related literature

For studies on the effects of substituents on the structures and other aspects of N-(aryl)-amides, see: Gowda et al. (2001 ▶); Kumar et al. (2012 ▶); Shahwar et al. (2012 ▶). For N-(aryl)-methanesulfonamides, see: Gowda et al. (2007 ▶). For N-chloroarylsulfonamides, see: Gowda & Ramachandra (1989 ▶), Shetty & Gowda (2004 ▶).

Experimental

Crystal data

C₉H₈Cl₂N₂OS
M _r = 263.13
Triclinic,
a = 7.8475 (6) Å
b = 9.5987 (7) Å
c = 15.141 (1) Å
α = 90.044 (6)°
β = 91.099 (6)°
γ = 100.208 (6)°
V = 1122.24 (14) Å³
Z = 4
Mo Kα radiation
μ = 0.74 mm⁻¹
T = 293 K
0.46 × 0.44 × 0.36 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.728, T _max = 0.777
7971 measured reflections
4578 independent reflections
3885 reflections with I > 2σ(I)
R _int = 0.011

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.106
S = 1.04
4578 reflections
285 parameters
4 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.67 e Å⁻³
Δρ_min = −0.72 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2009 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: PLATON (Spek, 2009 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812030176/bt5964sup1.cif

e-68-o2353-sup1.cif^{(25.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812030176/bt5964Isup2.hkl

e-68-o2353-Isup2.hkl^{(224.2KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812030176/bt5964Isup3.cml

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—H1N⋯O1	0.85 (2)	1.91 (2)	2.625 (3)	141 (3)
N2—H2N⋯S2	0.84 (2)	2.56 (2)	3.393 (2)	171 (2)
N3—H3N⋯O2	0.81 (2)	1.93 (2)	2.619 (3)	143 (3)
N4—H4N⋯S1	0.84 (2)	2.59 (2)	3.418 (2)	170 (2)

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Acknowledgments

BTG thanks the University Grants Commission, Government of India, New Delhi, for a special grant under the UGC-BSR one-time grant to faculty.

supplementary crystallographic information

Comment

As part of studies on the substituent effects on the structures and other aspects of N-(aryl)-amides (Gowda et al., 2001; Kumar et al., 2012: Shahwar et al., 2012); N-(aryl)-methanesulfonamides (Gowda et al., 2007) and N-chloroarylsulfonamides (Gowda & Ramachandra, 1989; Shetty & Gowda, 2004), in the present work, the crystal structure of 3-acetyl-1-(2,3-dichlorophenyl)thiourea has been determined (Fig. 1).

The asymmetric unit of the structure contains two molecules. The conformation of the two N—H bonds are anti to each other. Furthermore, the conformations of the amide C═S and the C═O are also anti to each other and both the bonds are anti to the adjacent N—H bonds, similar to the anti conformation observed in 3-acetyl-1-(2,3-dimethylphenyl)thiourea (I)(Kumar et al., 2012). The N—H bond adjacent to the 2,3-dichlorophenyl ring is syn to the ortho- and meta-Cl atoms in one of the molecules and anti in the other molecule, compared to the anti conformation observed with respect to the ortho- and meta-methyl groups in the 2,3-dimethylphenyl ring of (I).

The side chains are oriented themselves with respect to the 2,3-dichlorophenyl rings with the torsion angles, C2—C1—N1—C7 = 116.47 (26)° and C6—C1—N1—C7 = -65.77 (33)° in molecule 1 and C11—C10—N3—C16 = 129.96 (25)° and C15—C10—N3—C16 = -53.71 (35)° in molecule 2 of the title compound, compared to the torsion angles of C2—C1—N1—C7 = 83.59 (47)° and C6—C1—N1—C7 = -99.89 (44)° for in (I). The dihedral angles between the phenyl rings and the side chains are 62.5 (1)° and 51.3 (1)°, in the two molecules, compared to the value of 81.33 (10)° in (I).

The hydrogen atoms of the NH attached to the phenyl rings and the amide O atoms are involved in the intramolecular hydrogen bonding. In the crystal, the molecules form inversion dimers through pairs of N—H···S intermolecular hydrogen bonds (Table 1, Fig.2).

Experimental

3-Acetyl-1-(2,3-dichlorophenyl)thiourea was synthesized by adding a solution of acetyl chloride (0.10 mol) in acetone (30 ml) dropwise to a suspension of ammonium thiocyanate (0.10 mol) in acetone (30 ml). The reaction mixture was refluxed for 30 min. After cooling to room temperature, a solution of 2,3-dichloroaniline (0.10 mol) in acetone (10 ml) was added and refluxed for 3 h. The reaction mixture was poured into acidified cold water. The precipitated title compound was recrystallized to constant melting point from acetonitrile. The purity of the compound was checked and characterized by its infrared spectrum.

Prism like light yellow single crystals used in X-ray diffraction studies were grown in acetonitrile solution by slow evaporation of the solvent at room temperature.