Ethyl 2-(3-phenyl­thio­ureido)-5,6-di­hydro-4H-cyclo­penta­[b]thio­phene-3-carboxyl­ate

Jaismary G B de Oliveira; Francisco J B Mendonça Junior; Maria do Carmo A de Lima; Carlos A de Simone; Javier A Ellena

doi:10.1107/S1600536812029893

. 2012 Jul 7;68(Pt 8):o2360. doi: 10.1107/S1600536812029893

Ethyl 2-(3-phenylthioureido)-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carboxylate

Jaismary G B de Oliveira ^a, Francisco J B Mendonça Junior ^a, Maria do Carmo A de Lima ^b, Carlos A de Simone ^c,^*, Javier A Ellena ^c

PMCID: PMC3414293 PMID: 22904826

Abstract

In the title compound, C₁₇H₁₈N₂O₂S₂, the angle between the mean plane defined by the atoms of the 5,6-dihydro-4H-cyclopenta[b]thiophene moiety (r.m.s. deviation = 0.19 Å) and the phenyl ring is 72.8°(2). The molecular conformation is stabilized by an intramolecular N—H⋯O interaction, which generates an S(6) ring motif. In the crystal, pairs of N—H⋯S hydrogen bonds link the molecules to form inversion dimers with an R ₂ ²(8) ring motif.

Related literature

For background to 2-aminothiophene derivatives, see: Puterová et al. (2010 ▶). For the biological activity of 2-ureido- and 2-thioureido-thiophene-3-carboxylate derivatives, see: Arhin et al. (2006 ▶); Saeed et al. (2010 ▶). For the synthesis of 2-aminothiophenes, see: Gewald et al. (1966 ▶). For a related structure, see: Larson & Simonsen (1988 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶).

Experimental

Crystal data

C₁₇H₁₈N₂O₂S₂
M _r = 346.45
Triclinic,
a = 5.0755 (2) Å
b = 12.5088 (6) Å
c = 13.3304 (5) Å
α = 90.562 (3)°
β = 95.711 (3)°
γ = 94.378 (2)°
V = 839.61 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.33 mm⁻¹
T = 295 K
0.32 × 0.17 × 0.11 mm

Data collection

Nonius KappaCCD diffractometer
9172 measured reflections
3876 independent reflections
2727 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.045
wR(F ²) = 0.129
S = 1.04
3876 reflections
208 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: COLLECT (Nonius, 1997 ▶); cell refinement: SCALEPACK (Otwinowski & Minor, 1997 ▶); data reduction: DENZO (Otwinowski & Minor, 1997 ▶) and SCALEPACK; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536812029893/lr2068sup1.cif

e-68-o2360-sup1.cif^{(17.9KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812029893/lr2068Isup2.hkl

e-68-o2360-Isup2.hkl^{(179.8KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812029893/lr2068Isup3.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
N2—H2⋯S1ⁱ	0.86	2.61	3.415 (2)	157
N1—H1⋯O1	0.86	2.04	2.719 (2)	136

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Symmetry code: (i) Inline graphic .

Acknowledgments

This work has received partial support from CNPq, CAPES, FACEPE and FINEP. CADS thanks the Instituto de Física de São Carlos — USP for allowing the use of the KappaCCD diffractometer.

supplementary crystallographic information

Comment

The various uses and applications of 2-amino thiophene derivatives have been well documented (Puterová et al., 2010). Amongst these appplications, 2-thioureido-thiophene derivatives presents antifungal (Saeed et al., 2010) and antibacterial activities (Arhin et al., 2006). In this work, we report the structure of the title compound prepared by the condensation of 2-amino-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile with phenyl isothiocyanate.

The angle between the least-squares plane defined by the atoms of the 5,6-dihydro-4H-cyclopenta[b]thiophene moiety (rms deviation=0.19 Å) and the phenyl rings is 72.8°(2). There is an intramolecular N—H···O interaction giving an S(6) ring motif. In the crystal N—H···S hydrogen-bond interactions link the molecules into pairs giving an R₂²(8) motif which extends parallel to the plane (120). (Table 2, Fig.2).

Experimental

Equimolar amounts of 2-amino-5,6-dihydro-4H-cyclopenta[b]thiophene-3-carbonitrile (4.19 mmol) and phenyl isothiocyanate (4.19 mmol) were heated under reflux for 16 h, in the presence of dry toluene (10 ml), and 5 drops of trietylamine. The solid product formed was collected by filtration, washed with ethyl acetate (3 x 10 ml) and crystallized from absolute etanol, affording the title compound as pale yellow crystals (1.07 g, 74%), M.p. 185–187 °C. Crystals suitable for single-crystal X-ray diffraction were grown by slow evaporation at room temperature of a solution of the pure title compound in absolute ethanol. NMR ¹H (400 MHz, CDCl₃)δ: 1.25 (t, 3H, J = 6.4 Hz), 2.28 (d, 2H, J = 6.0 Hz), 2.76–2.81 (m, 4H), 4.20 (d, 2H, J = 6.0 Hz), 7.24 (s, 1H), 7.39 (d, 2H, J = 6.8 Hz), 7.48 (d, 2H, J = 7.2 Hz), 11.00 (bs, 1H); 11.58 (bs, 1H).