1-(4-Acetyl­phen­yl)-3-butyrylthio­urea

Sohail Saeed; Moazzam Hussain Bhatti; Uzma Yunus; Peter G Jones

doi:10.1107/S1600536808022095

. 2008 Jul 23;64(Pt 8):o1566. doi: 10.1107/S1600536808022095

1-(4-Acetylphenyl)-3-butyrylthiourea

Sohail Saeed ^a,^*, Moazzam Hussain Bhatti ^a, Uzma Yunus ^a, Peter G Jones ^b

PMCID: PMC2962175 PMID: 21203269

Abstract

The title compound, C₁₃H₁₆N₂O₂S, crystallizes in the thioamide form with an intramolecular hydrogen bond of type N—H⋯O_butyryl. Molecules are linked into chains parallel to [10 Inline graphic ] by a further hydrogen bond of type N—H⋯O_acetyl. C—H⋯O and C—H⋯S hydrogen bonds are also present.

Related literature

For related literature, see: D’hooghe et al. (2005 ▶); Glasser & Doughty (1964 ▶); Huebner et al. (1953 ▶); Jain & Rao (2003 ▶); Morales et al. (2000 ▶); Ru et al. (1994 ▶); Xu et al. (2004 ▶); Xue et al. (2003 ▶); Zeng et al. (2003 ▶); Zheng et al. (2004 ▶); Douglas & Dains (1934 ▶).

Experimental

Crystal data

C₁₃H₁₆N₂O₂S
M _r = 264.34
Triclinic,
a = 7.5111 (5) Å
b = 9.7585 (8) Å
c = 10.5036 (5) Å
α = 65.283 (5)°
β = 76.245 (4)°
γ = 68.589 (5)°
V = 647.78 (8) Å³
Z = 2
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 100 (2) K
0.35 × 0.20 × 0.10 mm

Data collection

Oxford Diffraction Xcalibur S diffractometer
Absorption correction: multi-scan (CrysAlis RED; Oxford Diffraction, 2008 ▶) T _min = 0.940, T _max = 0.976
22401 measured reflections
3613 independent reflections
3036 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.087
S = 1.06
3613 reflections
173 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2008 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2008 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: XP (Siemens, 1994 ▶); software used to prepare material for publication: SHELXL97.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808022095/pk2104sup1.cif

e-64-o1566-sup1.cif^{(17.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808022095/pk2104Isup2.hkl

e-64-o1566-Isup2.hkl^{(177.1KB, 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—H02⋯O1	0.840 (16)	1.874 (16)	2.6211 (12)	147.4 (16)
N1—H01⋯O2ⁱ	0.835 (16)	2.087 (16)	2.9057 (12)	166.7 (13)
C3—H3B⋯O2ⁱ	0.99	2.54	3.1345 (13)	118
C1—H1C⋯Sⁱⁱ	0.98	3.01	3.8996 (13)	151
C3—H3A⋯Sⁱⁱ	0.99	2.92	3.8444 (11)	155

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

Acknowledgments

The authors are grateful to Allama Iqbal Open University, Islamabad, Pakistan, for the allocation of research and analytical laboratory facilities.

supplementary crystallographic information

Comment

Thiourea and its derivatives have found extensive applications in the fields of medicine, agriculture and analytical chemistry. Substituted thioureas are an important class of compounds, precursors or intermediates towards the synthesis of a variety of heterocyclic systems such as imidazole-2-thiones (Zeng et al., 2003), 2-imino-1, 3-thiazolines (D'hooghe et al., 2005) pyrimidines-2-thione (Jain & Rao, 2003) and (benzothiazolyl)-4-quinazolinones. N– (Substituted phenyl)-N-phenylthioureas and N– (substituted butanoyl)-N-phenylthioureas have been developed. Thioureas are also known to exhibit a wide range of biological activities including antiviral, antibacterial, antifungal, (Huebner et al., 1953) antitubercular, antithyroidal, herbicidal and insecticidal activities and as agrochemicals (Xu et al., 2004), e.g. 1-benzoyl-3-(4,5-disubstituted-pyrimidine-2-yl)- thioureas, which have excellent herbicidal activity (Zheng et al., 2004). Thioureas are also well known chelating agents for transition metals (Xue et al., 2003). N,N-Dialkyl-N'-benzoyl thioureas act as selective complexing agents for the enrichment of platinum metals even from strongly interfacing matrixes (Ru et al., 1994). The complexes of thiourea derivatives also show various biological activities (Glasser & Doughty, 1964). Thioureas and substituted thioureas are also known as epoxy resin curing agents.

The title compound is a precursor for an attempt to synthesize imidazole derivatives and transition metal complexes as epoxy resin curing agents and accelerators. It crystallizes in the thioamide form (Fig. 1). The molecule is essentially planar (r.m.s. deviation of all non-H atoms 0.118 (1) Å), as reflected by the torsion angles O1—C4—N1—C5, C4—N1—C5—S and C4—N1—C5—N2 of 0.85 (17)°, 174.53 (8)° and -5.70 (15)°, respectively. The C4—O1, C5—S and C12—O2 bonds show a typical double bond character with bond lengths of 1.2246 (13), 1.6629 (11) and 1.2243 (13) Å, respectively. All the C—N bonds, C4—N1 = 1.3864 (13), C6—N2 = 1.4061 (12), C5—N2 = 1.3458 (13) and C5—N1 = 1.3948 (12) Å display a partial double bond character. Among the latter three C—N bonds, C4—N1 is the longest indicating a C(sp²)—N(sp²) single bond, while C5—N2 is the shortest bond with more double bond character. This demonstrates that there is π conjugation along S—C5—N2 but not along O1—C4—N1 and C4—N1—C5 as found in 1-(3-methoxybenzoyl)-3, 3-diethylthiourea (Morales et al., 2000). There is a strong intramolecular hydrogen bond N2—H02···O1, with H2···O1 = 1.874 (16) Å, forming a 6-membered ring.

Molecules are connected in chains parallel to [101] by classical hydrogen bonds N1—H1···O2 and a weak bifurcated component C3—H3B···O2; the chains are further connected in an antiparallel sense by a bifurcated system of two C—H···S contacts (Table 2, Fig. 2).

Experimental

The title compound was synthesized by a slight modification of the published procedure (Douglas & Dains, 1934). A solution of butanoyl chloride (0.1 mol) in dry acetone (75 ml) was added dropwise to a suspension of ammonium thiocyanate (0.1 mol) in dry acetone (55 ml) and the reaction mixture was refluxed for 45 minutes. After cooling to room temperature, a solution of 4-aminoacetophenone (0.1 mol) in dry acetone (25 ml) was added and the resulting mixture refluxed for 1.5 hrs. The reaction mixture was poured into five times its volume of cold water whereupon the thiourea precipitated as a solid. The product was recrystallized from ethyl acetate as colourless crystals (2.85 g, 79%). m.p.458 K.