1-Furoyl-3-[3-(trifluoro­meth­yl)phen­yl]thio­urea

Jahyr E Theodoro; O Estévez-Hernández; J Ellena; J Duque; Rodrigo S Corrêa

doi:10.1107/S1600536809013038

. 2009 Apr 10;65(Pt 5):o1012. doi: 10.1107/S1600536809013038

1-Furoyl-3-[3-(trifluoromethyl)phenyl]thiourea

Jahyr E Theodoro ^a, O Estévez-Hernández ^b,^*, J Ellena ^a, J Duque ^b, Rodrigo S Corrêa ^a

PMCID: PMC2977699 PMID: 21583835

Abstract

The title compound, C₁₃H₉F₃N₂O₂S, crystallizes with two independent molecules in the asymmetric unit. The central thiourea core is roughly coplanar with the furan and benzene rings, showing O—C—N—C(S) torsion angles of 2.3 (4) and −11.4 (2)° and (S)C—N—C—C torsion angles of −2.4 (4) and −28.8 (4)°, respectively, in the two independent molecules. The trans–cis geometry of the thiourea fragment is stabilized by an intramolecular N—H⋯O hydrogen bond between the H atom of the cis thioamide and the carbonyl O atom. In the crystal structure, intermolecular N—H⋯S hydrogen bonds form centrosymmetric dimers extending along the b axis.

Related literature

For general background to aroylthioureas, see: Aly et al. (2007 ▶); Koch (2001 ▶); Estévez-Hernández et al. (2007 ▶); Otazo-Sánchez et al. (2002 ▶). For related structures, see: Theodoro et al. (2008 ▶); Pérez et al. (2008 ▶). For the synthesis, see: Otazo-Sánchez et al. (2001 ▶).

Experimental

Crystal data

C₁₃H₉F₃N₂O₂S
M _r = 314.29
Triclinic,
a = 7.5540 (14) Å
b = 13.684 (5) Å
c = 14.210 (3) Å
α = 86.124 (13)°
β = 74.779 (7)°
γ = 74.065 (8)°
V = 1362.9 (6) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 294 K
0.09 × 0.07 × 0.03 mm

Data collection

Enraf–Nonius KappaCCD diffractometer
Absorption correction: none
9271 measured reflections
4953 independent reflections
2925 reflections with I > 2σ(I)
R _int = 0.035

Refinement

R[F ² > 2σ(F ²)] = 0.044
wR(F ²) = 0.123
S = 1.01
4953 reflections
433 parameters
H-atom parameters constrained
Δρ_max = 0.14 e Å⁻³
Δρ_min = −0.24 e Å⁻³

Data collection: COLLECT (Nonius, 2000 ▶); 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 ▶) and Mercury (Macrae et al., 2006 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809013038/fj2202sup1.cif

e-65-o1012-sup1.cif^{(24.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809013038/fj2202Isup2.hkl

e-65-o1012-Isup2.hkl^{(237.6KB, 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
N1—H1⋯S1Aⁱ	0.86	2.78	3.643 (2)	176
N1—H1⋯O2	0.86	2.27	2.692 (3)	110
N1A—H1A⋯S1ⁱⁱ	0.86	2.74	3.592 (2)	173
N1A—H1A⋯O2A	0.86	2.30	2.700 (3)	108
N2—H2⋯O1	0.86	1.88	2.625 (3)	144
N2A—H2A⋯O1A	0.86	1.92	2.640 (3)	140

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

Acknowledgments

The authors acknowledge financial support from the Brazilian agency CNPq. OEH thanks CONACyT of Mexico for research grant No. 61541.

supplementary crystallographic information

Comment

The importance of aroylthioureas is found largely in heterocyclic syntheses and many of these substrates have interesting biological activities. Aroylthioureas have also been found to have applications in metal complexes and molecular electronics (Aly et al., 2007). The title compound (I), Fig. 1, was synthesized from furoyl isothiocyanate and 3-trifluorometylaniline in dry acetone. This thiourea derivative has been successfully used as ionophore in amperometric sensor for Cd(II) (Estévez-Hernández et al., 2007). The title compound crystallizes in the thioamide form with two independent molecules in the asymmetric unit. The main bond lengths are within the ranges obtained for similar compounds (Koch et al., 2001 and Pérez et al., 2008). The C2—S1 and C1—O1 bonds (Table 1) both show the expected double-bond character. The short values of the C2—N1, C2—N2 and C1—N2 bonds indicate partial double bond character. These results can be explained by the existence of resonance in this part of the molecule. The C=S distance for compound I (two unique molecules) averages 1.648 Å. The furan carbonyl (O1—C1—C3—O2 and O1a—C1a—C3a—O2a, two unique molecules) groups are inclined 2.3 (4)° and -11.4 (2)° with respect to the plane formed by the thiourea moiety (N1—C2—S1—N2 and N1a—C2a—S2—N2a, two unique molecules)in each molecule, while the 3-trifluoromethylphenyl (C7—C8—C9—C10—C11 and C7a—C8a—C9a—C10a—C11a, two unique molecules) rings are inclined -2.4 (4)° and -28.8 (4)°, respectively. In addition, the dihedral angles of two independent molecules between the furan and benzene ring planes are 18.91 (1)° and 14.78 (1)°, respectively. The trans-cis geometry in the thiourea moiety is stabilized by the N2—H2···.O1 intramolecular hydrogen bond. This strong interaction is also observed in solution (Otazo-Sánchez et al., 2002) and locks the –CONHCSNHR– unit into a stable planar six-membered ring structure (Fig.1 and Table 1). In this S-shaped conformation between the C=O and C=S groups (two donors sites rich in electron density), the O—S distance is maximum, contributing to a minimum conformational energy of the molecule as a whole (Koch et al., 2001). Another weaker intramolecular hydrogen interaction between the furan oxygen atom O2 and the N1—H1 hydrogen atom is observed. The crystal structure is stabilized by two intermolecular N1—H1···.S1 hydrogen bonds (Fig.2 and Table 1) between related molecules forming dimers pilled within the unit cell along the [010] direction.

Experimental

The title compound (I) was synthesized according to a previous report (Otazo-Sánchez et al., 2001), by converting furoyl chloride into furoyl isothiocyanate and then condensing with 3-trifluorometylaniline. The resulting solid product was crystallized from ethanol yielding X-ray quality single crystals (m.p 112–113 °C). Elemental analysis (%) for C₁₃H₉N₂O₂F₃S calculated: C 49.68, H 2.87, N 8.92, S 10.19; found: C 49.46, H 2.86, N 15.79, S 10.09.