Redetermination of 1-benzyl-3-furoyl-1-phenyl­thio­urea

O Estévez-Hernández; Rodrigo S Corrêa; J Ellena; J Duque

doi:10.1107/S1600536808044085

. 2009 Feb 28;65(Pt 3):o648. doi: 10.1107/S1600536808044085

Redetermination of 1-benzyl-3-furoyl-1-phenylthiourea

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

PMCID: PMC2968693 PMID: 21582296

Abstract

The title compound, C₁₉H₁₆N₂O₂S, was synthesized from furoyl isothiocyanate and N-benzylaniline in dry acetone and the structure redetermined. The structure [Otazo-Sánchez et al. (2001 ▶). J. Chem. Soc. Perkin Trans. 2, pp. 2211–2218] has been re-determined in order to establish the intramolecular and intermolecular interactions. The thiourea group is in the thioamide form. The thiourea group makes a dihedral angle of 29.2 (6)° with the furoyl group. In the crystal structure, molecules are linked by intermolecular C—H⋯O interactions, forming one-dimensional chains along the a axis. An intramolecular N—H⋯O hydrogen bond is also present.

Related literature

For general background, see: Aly et al. (2007 ▶), Koch (2001 ▶), Estévez-Hernández et al. (2006 ▶). For related structures, see: Pérez et al. (2008 ▶). For the synthesis, see: Otazo-Sánchez et al. (2001 ▶).

Experimental

Crystal data

C₁₉H₁₆N₂O₂S
M _r = 336.41
Orthorhombic,
a = 12.7737 (3) Å
b = 8.8047 (2) Å
c = 31.2345 (7) Å
V = 3512.90 (14) Å³
Z = 8
Mo Kα radiation
μ = 0.20 mm⁻¹
T = 294 (2) K
0.54 × 0.22 × 0.19 mm

Data collection

Nonius KappaCCD diffractometer
Absorption correction: gaussian (Coppens et al., 1965 ▶) T _min = 0.92, T _max = 0.971
19732 measured reflections
3536 independent reflections
2565 reflections with I > 2σ(I)
R _int = 0.058

Refinement

R[F ² > 2σ(F ²)] = 0.041
wR(F ²) = 0.114
S = 1.03
3536 reflections
281 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.12 e Å⁻³
Δρ_min = −0.13 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 (Bruno et al., 2002 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536808044085/bq2112sup1.cif

e-65-0o648-sup1.cif^{(18.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808044085/bq2112Isup2.hkl

e-65-0o648-Isup2.hkl^{(170KB, 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⋯O2	0.84 (2)	2.25 (2)	2.677 (2)	111 (2)
C6—H6⋯O1ⁱ	0.92 (2)	2.40 (2)	3.315 (3)	172 (2)
C8—H8⋯O1ⁱⁱ	0.92 (2)	2.57 (2)	3.242 (2)	131 (2)

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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 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, Estévez-Hernández et al., 2006). The structure of the title compound (I), Fig.1, has been redetermined and the result adds significantly to the information already in the public domain (Otazo-Sánchez et al., 2001), especially about the intra and intermolecular interactions (not reported previously). The data and the refinement of the structure are also of better quality (present refinement: R: 0.0410 and wR: 0.1137; previous refinement: R: 0.1450 and wR: 0.2356). The main bond lengths and angles are within the ranges obtained for similar compounds (Koch et al., 2001; Pérez et al., 2008). The C2—S1 and C1—O1 bonds show typical double-bond character. However, the C—N bond lengths, C1—N1, C2—N1, C2—N2 are shorter than the normal C—N single-bond length of about 1.48 Å. These results can be explained by the existence of resonance in this part of the molecule. The central thiourea fragment (N1—C2—S1—N2) makes dihedral angle of 29,2(6)° with the furan carbonyl (O1—O2—C1—C3—C6) group, whereas the C7—C12 benzene ring is inclined by 84,7(6)°. The crystal structure is stabilized principally by the intramolecular N1—H···O2 hydrogen bond (Fig.1 and Table 1). In the crystal structure symmetry related molecules are linked by two different C—H···O1 interactions (C8—H···O1, 3.2<D<3.6 Å and θ>110°) and (C6—H···O1, 3.2<D<3.6 Å and θ>150°) to form one-dimensional chains along the a-axis (Fig. 2 and Table 1).

Experimental

The title compound, (I), was synthesized according to a procedure described by Otazo-Sánchez et al. (2001), by converting furoyl chloride into furoyl isothiocyanate and then condensing with N-benzylaniline. The resulting solid product was crystallized from ethanol yielding X-ray quality single crystals (m.p. 127–128°C). Elemental analysis for C₁₉H₁₆N₂O₂S found: C 59.95, H 4.60, N 10.74, S 11.21%; calculated: C 60.00, H 4.62, N 10.76, S 11.31%.