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

B Thimme Gowda; Sabine Foro; Sharatha Kumar

doi:10.1107/S1600536812032825

. 2012 Jul 28;68(Pt 8):o2574. doi: 10.1107/S1600536812032825

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

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

PMCID: PMC3415014 PMID: 22905001

Abstract

In the crystal structure of the title compound, C₁₀H₁₂N₂OS, the conformation of the two N—H bonds are anti to each other. The amide C=O and the C=S are are also anti to each other. The N—H bond adjacent to the benzene ring is syn to the m-methyl groups. The dihedral angle between the benzene ring and the side chain [mean plane of atoms C—C(O)N—C—N; maximum deviation 0.029 (2) Å] is 14.30 (7)°. There is an intramolecular N—H⋯O hydrogen bond generating an S(6) ring motif. In the crystal, the molecules are linked via N—H⋯) hydrogen bonds, forming chains propagating along [001]. The S atom is disordered and was refined using a split model [occupancy ratio 0.56 (4):0.44 (4)].

Related literature

For studies on the effects of substituents on the structures and other aspects of N-(aryl)-amides, see: Alkan et al. (2011 ▶); Bhat & Gowda (2000 ▶); Bowes et al. (2003 ▶); Gowda et al. (2000 ▶); Saeed et al. (2010 ▶); Shahwar et al. (2012 ▶), of N-(aryl)-methanesulfonamides, see: Gowda et al. (2007 ▶) and of N-chloroarylsulfonamides, see: Gowda & Ramachandra (1989 ▶); Jyothi & Gowda (2004 ▶); Shetty & Gowda (2004 ▶).

Experimental

Crystal data

C₁₀H₁₂N₂OS
M _r = 208.29
Monoclinic,
a = 7.6841 (9) Å
b = 14.943 (1) Å
c = 9.5358 (9) Å
β = 107.49 (1)°
V = 1044.32 (18) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 295 K
0.48 × 0.44 × 0.24 mm

Data collection

Oxford Diffraction Xcalibur Sapphire CCD. diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2009 ▶) T _min = 0.878, T _max = 0.936
4011 measured reflections
2137 independent reflections
1789 reflections with I > 2σ(I)
R _int = 0.011

Refinement

R[F ² > 2σ(F ²)] = 0.035
wR(F ²) = 0.100
S = 1.06
2137 reflections
145 parameters
2 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.17 e Å⁻³
Δρ_min = −0.22 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/S1600536812032825/rk2375sup1.cif

e-68-o2574-sup1.cif^{(19KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812032825/rk2375Isup2.hkl

e-68-o2574-Isup2.hkl^{(105.1KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812032825/rk2375Isup3.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	0.87 (1)	1.90 (2)	2.6536 (16)	144 (2)
N2—H2N⋯O1ⁱ	0.85 (1)	2.12 (1)	2.9564 (16)	166 (2)

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Symmetry code: (i) Inline graphic .

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 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 (Alkan et al., 2011; Bhat & Gowda, 2000; Bowes et al., 2003; Gowda et al., 2000; Saeed et al., 2010; Shahwar et al., 2012); N-(aryl)-methanesulfonamides (Gowda et al., 2007) and N-chloroarylamides (Gowda & Ramachandra, 1989; Jyothi & Gowda, 2004; Shetty & Gowda, 2004), in the present work, the crystal structure of 3-acetyl-1-(3-methylphenyl)thiourea, has been determined (Fig. 1).

The conformation of the two N–H bonds are anti to each other. The adjacent N–H bond is syn to the m-methyl group in the benzene ring, compared to the anti conformation observed between the N–H bond and the o-methyl group in the benzene ring in 3-acetyl-1-(2-methylphenyl)thiourea, I, (Shahwar et al., 2012). Furthermore, the conformation of the amide C═O and the C═S are anti to each other, similar to that observed in I.

The side chain is oriented itself with respect to the phenyl ring with the torsion angles of C2—C1–N1—C7 = -168.76 (14)° and C6—C1—N1—C7 = 14.71 (24)°. The dihedral angle between the phenyl ring and the side chain (N1/C7/N2/C8/O1/C9) is 14.30 (7)°.

The amide oxygen exhibits a bifurcated hydrogen bonding by showing the simultaneous intra- and intermolecular hydrogen bonding generating S(6) and C(4) motifs. In the crystal of the title compound, the molecules are linked via N—H···S hydrogen bonds with an R₂²(12) motif and N—H···O hydrogen bonds with a C(4) motif into a layered structure (Table 1, Fig. 2).

Experimental

3-Acetyl-1-(3-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 3-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. The characteristic absorptions observed are 3163.7 cm^-1, 1690.0 cm^-1, 1269.5 cm^-1 and 693.3 cm^-1 for the stretching bands of N-H, C═O, C-N and C═S, respectively.

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.