3-Acetyl-1-(4-methyl­phen­yl)thio­urea

B Thimme Gowda; Sabine Foro; Sharatha Kumar

doi:10.1107/S1600536812026244

. 2012 Jun 16;68(Pt 7):o2128. doi: 10.1107/S1600536812026244

3-Acetyl-1-(4-methylphenyl)thiourea

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

PMCID: PMC3393939 PMID: 22798804

Abstract

The asymmetric unit of the title compound, C₁₀H₁₂N₂OS, contains two independent molecules. In both molecules, the conformations of the two N—H bonds are anti to each other. Furthermore, the conformations of the amide C=S bonds and the C=O bonds are anti to each other. The dihedral angles between the benzene ring and the side chain are 52.8 (1) and 68.0 (1)° in the two independent molecules. An intramolecular N—H⋯O hydrogen bond occurs in both independent molecules. In the crystal, molecules are linked into infinite chains along the a axis through a series of N—H⋯O and N—H⋯S hydrogen bonds.

Related literature

For studies on the effects of substituents on the structures and other aspects of N-(aryl)-amides, see: Gowda & Weiss (1994 ▶); Shahwar et al. (2012 ▶), of N-(aryl)-methanesulfonamides, see: Gowda et al. (2007 ▶), of N-(aryl)-arylsulfonamides, see: Gowda et al. (2005 ▶) and of N-chloroarylsulfonamides, see: Jyothi & Gowda (2004 ▶); Shetty & Gowda (2004 ▶).

Experimental

Crystal data

C₁₀H₁₂N₂OS
M _r = 208.28
Triclinic,
a = 9.1623 (8) Å
b = 10.130 (1) Å
c = 13.446 (1) Å
α = 73.212 (9)°
β = 70.276 (8)°
γ = 66.772 (8)°
V = 1061.90 (16) Å³
Z = 4
Mo Kα radiation
μ = 0.27 mm⁻¹
T = 293 K
0.36 × 0.32 × 0.24 mm

Data collection

Oxford Diffraction Xcalibur diffractometer with a Sapphire CCD detector
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.908, T _max = 0.937
7674 measured reflections
4293 independent reflections
3267 reflections with I > 2σ(I)
R _int = 0.013

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.112
S = 1.00
4293 reflections
257 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.26 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2009 ▶); cell refinement: CrysAlis CCD; data reduction: CrysAlis RED (Oxford Diffraction, 2009 ▶); 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/S1600536812026244/nc2284sup1.cif

e-68-o2128-sup1.cif^{(28.3KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812026244/nc2284Isup2.hkl

e-68-o2128-Isup2.hkl^{(210.4KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812026244/nc2284Isup3.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	0.84	2.02	2.674 (2)	134
N1—H1N⋯O2ⁱ	0.84	2.47	3.198 (2)	145
N2—H2N⋯S2ⁱⁱ	0.84	2.68	3.5058 (17)	169
N3—H3N⋯O2	0.86	1.97	2.661 (2)	137
N3—H3N⋯O1ⁱ	0.86	2.42	3.131 (2)	140
N4—H4N⋯S1ⁱⁱ	0.85	2.57	3.4078 (17)	169

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

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

Thiourea and its derivatives are widely used as precursors or intermediates towards the syntheisis of a variety of heterocyclic compounds. They are known to exhibit a wide variety of biological activities. As part of our studies on the substituent effects on the structures and other aspects of N-(aryl)-amides (Gowda & Weiss, 1994); N-(aryl)-methanesulfonamides (Gowda et al., 2007); N-(aryl)-arylsulfonamides (Gowda et al., 2005) and N-chloroarylsulfonamides (Jyothi & Gowda, 2004; Shetty & Gowda, 2004). in the present work, the crystal structure of 3-acetyl-1-(4-methylphenyl)thiourea has been determined (Fig. 1).

The asymmetric unit of the structure contains two independent molecules. The conformations of the two N—H bonds in the side chain are anti to each other and one of them is anti to the C═S in the urea segments and the other is syn, in both the molecules, similar to the anti conformation observed in 3-acetyl-1-(2-methylphenyl)thiourea (Shahwar et al., 2012) Further, the conformations of the amide C═S and the C═O are anti to each other.

The side chains are oriented themselves with respect to the phenyl rings with the torsion angles of C2—C1—N1—C7 = 53.32 (32)° and C6—C1—N1—C7 = - 131.28 (24)° in molecule 1, and C12—C11—N3—C17 = - 67.14 (31)° and C16—C11—N3—C17 = 116.61 (26)° in molecule 2. The dihedral angles between the phenyl rings and the side chains are 52.8 (1)° and 68.0 (1)°, in the two independent molecules.

The amide oxygen and one of the NH hydrogen atoms exhibit both intra- and inter-molecular bifurcated hydrogen bonding. In the structure, series of N—H···O and N—H···S intermolecular hydrogen bonds pack the molecules into infinite chains (Table 1, Fig.2).

Experimental

3-Acetyl-1-(4-methylphenyl)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 4-methylaniline (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 yellow single crystals used in X-ray diffraction studies were grown in acetonitrile solution by slow evaporation of the solvent at room temperature.