1-(6-Methyl-3-phenyl-2-sulfanyl­idene-1,2,3,4-tetra­hydro­pyrimidin-5-yl)ethanone

Emin N Garibov; Sevinj S Gojayeva; Mirze A Allahverdiyev; Atash V Gurbanov Gurbanov; Iván Brito

doi:10.1107/S1600536811055309

. 2012 Jan 7;68(Pt 2):o276. doi: 10.1107/S1600536811055309

1-(6-Methyl-3-phenyl-2-sulfanylidene-1,2,3,4-tetrahydropyrimidin-5-yl)ethanone

Emin N Garibov ^a, Sevinj S Gojayeva ^a, Mirze A Allahverdiyev ^a, Atash V Gurbanov Gurbanov ^a, Iván Brito ^b,^*

PMCID: PMC3274973 PMID: 22346918

Abstract

In the title compound, C₁₃H₁₄N₂OS, four C atoms of the phenyl ring are disordered over two sets of sites in a 0.60 (3):0.40 (3) ratio. The heterocyclic ring is essentially planar (r.m.s. deviation = 0.017 Å) and forms dihedral angles of 82.0 (2) and 79.3 (3)°, respectively, with the major and minor occupancy components of the phenyl ring. The crystal packing features N—H⋯O hydrogen bonds, which link the molecules into C(6) chains running parallel to the b axis.

Related literature

For synthetic methods, see: Kotharkar et al. (2006 ▶); Lu et al. (2000 ▶); Salehi et al. (2003 ▶); Srinivas & Das (2004 ▶). For pharmacological properties of related compounds, see: Dalinger et al. (2004 ▶). For graph-set notation see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₃H₁₄N₂OS
M _r = 246.32
Orthorhombic,
a = 24.3527 (10) Å
b = 7.2374 (3) Å
c = 7.0063 (3) Å
V = 1234.86 (9) Å³
Z = 4
Mo Kα radiation
μ = 0.25 mm⁻¹
T = 100 K
0.30 × 0.30 × 0.30 mm

Data collection

Bruker APEXII CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2003 ▶) T _min = 0.930, T _max = 0.930
13745 measured reflections
3089 independent reflections
2877 reflections with I > 2σ(I)
R _int = 0.016

Refinement

R[F ² > 2σ(F ²)] = 0.051
wR(F ²) = 0.141
S = 1.00
3089 reflections
150 parameters
19 restraints
H-atom parameters constrained
Δρ_max = 0.40 e Å⁻³
Δρ_min = −0.35 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT-Plus (Bruker, 2001 ▶); data reduction: SAINT-Plus; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536811055309/lr2042sup1.cif

e-68-0o276-sup1.cif^{(19.8KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811055309/lr2042Isup2.hkl

e-68-0o276-Isup2.hkl^{(151.6KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811055309/lr2042Isup3.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
N3—H3N⋯O1ⁱ	0.88	2.05	2.920 (2)	168

Open in a new tab

Symmetry code: (i) Inline graphic .

Acknowledgments

The authors thank Baku State University and the Universidad de Antofagasta for supporting this study. Thanks are also given to the Consejo Superior de Investigaciones Científicas (CSIC) of Spain for the award of a license for the use of the Cambridge Structural Database (CSD).

supplementary crystallographic information

Comment

The dihydropyrimidinethiones display many pharmacological properties (Dalinger et al. 2004), as part of our interest in this kind of materials, we report here the synthesis and crystal structure determination of the title compound. Our synthesis is based in the Bidjinelli reaction, which consists on a three-component condensation of an aldehyde, a methylene active compound and an thiourea derivative in acidic media. This procedure is the most simple and useful for the preparation of 3,4-dihydropyrimidene-2(1H) thiones (Kotharkar et al. 2006; Lu et al. 2000; Srinivas & Das, 2004; Salehi et al. 2003).

In the compound, the C8, C9, C11 and C12 atoms of the phenyl ring are disordered over two sets of sites in a 0.60 (3):0.40 (3) ratio. The heterocycle ring is essentially planar (r.m.s.= 0.017 Å) and form a dihedral angle of 82.0 (2)° with the phenyl ring.The crystal packing is stabilized by intermolecular N3—H3N···O1 hydrogen bonds (Table 1), which link the molecules into chains running parallel to the b axis (Fig.2), with graph-set notation C(6), (Bernstein et al. 1995).

Experimental

Phenylthiourea, 15.2 g (0.1 mol), 37% water solution of formaldehyde (formaline), 3 g (0.1 mol) and 13 g (0.1 mol) of acetoacetic ester were dissolved in 10 ml of ethanol and then 0.5 ml of trifluoroacetic was added. The mixture was vigorously stirred during 4–5 h at room temperature and then cooled and kept one day at 0°C. The white crystals of 1-(6-methyl-3-phenyl-2-thioxo-1,2,3,4-tetrahydropyrimidin-5-yl) ethanone were filtered and washed with dichloromethane. Suitable crystal for diffraction were obtained by slow evaporation from ethanol. The yield was of 19.2 g (70%). Mp 180°C. R_f = 0.35. Eluent- ethanol:hexane (5:2). ¹H NMR (300 MHz, DMSO-d6) δ 1.35 (s, 3H, CH₃), 6.8–7.1 (m, H, Ar), 7.4 (m, H, Ar), 9.35 (s, 1H, NH). ¹³C NMR (75 MHz, DMSO-d6) δ 24, 29, 37, 51, 86, 117, 122, 129, 132, 141, 151, 179 (C=S), 205 (C=O)