N-(2-Furo­yl)-N′-(2-pyrid­yl)thio­urea

O Estévez-Hernández; J Duque; H Pérez; S Santos Jr; Y Mascarenhas

doi:10.1107/S1600536809011301

. 2009 Mar 31;65(Pt 4):o929–o930. doi: 10.1107/S1600536809011301

N-(2-Furoyl)-N′-(2-pyridyl)thiourea

O Estévez-Hernández ^a,^*, J Duque ^a, H Pérez ^b, S Santos Jr ^c, Y Mascarenhas ^d

PMCID: PMC2968930 PMID: 21582630

Abstract

The title compound, C₁₁H₉N₃O₂S, crystallizes with two independent molecules in the asymmetric unit. The central thiourea core makes dihedral angles of −3.3 (3) and 0.6 (3)° with the furan carbonyl groups in each molecule, whereas the pyridine ring is inclined by 4.63 (2) and 11.28 (7)°, respectively. The trans–cis geometry of the thiourea fragment is stabilized by an intramolecular N—H⋯N hydrogen bond between the H atom of the cis-thioamide group and the pyridine N atom. In the crystal structure, intermolecular bifurcated N—H⋯S and N—H⋯O hydrogen bonds form centrosymmetric tetramers extending along the b axis.

Related literature

For general background, see: Aly et al. (2007 ▶); Su et al. (2006 ▶). For related structures, see: Duque et al. (2008 ▶); Corrêa et al. (2008 ▶); Theodoro et al. (2008 ▶); Valdés-Martínez et al. (2002 ▶); Koch (2001 ▶); Pérez et al. (2008 ▶). For the synthesis, see: Otazo-Sánchez et al. (2001 ▶).

Experimental

Crystal data

C₁₁H₉N₃O₂S
M _r = 247.27
Monoclinic,
a = 6.9510 (1) Å
b = 15.7000 (4) Å
c = 20.2700 (6) Å
β = 90.284 (2)°
V = 2212.05 (9) Å³
Z = 8
Mo Kα radiation
μ = 0.29 mm⁻¹
T = 150 K
0.12 × 0.08 × 0.06 mm

Data collection

Enraf–Nonius KappaCCD diffractometer
Absorption correction: none
22281 measured reflections
4337 independent reflections
3574 reflections with I > 2σ(I)
R _int = 0.060

Refinement

R[F ² > 2σ(F ²)] = 0.042
wR(F ²) = 0.122
S = 1.10
4337 reflections
323 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.45 e Å⁻³
Δρ_min = −0.46 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/S1600536809011301/ng2563sup1.cif

e-65-0o929-sup1.cif^{(21.1KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809011301/ng2563Isup2.hkl

e-65-0o929-Isup2.hkl^{(208.2KB, 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	0.89 (2)	2.23 (2)	2.653 (2)	109.3 (18)
N1—H1⋯N3	0.89 (2)	1.84 (2)	2.612 (2)	145 (2)
N1A—H1A⋯O2A	0.87 (2)	2.22 (2)	2.661 (2)	111.6 (18)
N1A—H1A⋯N3A	0.87 (2)	1.90 (2)	2.632 (2)	141 (2)
N2—H2⋯O1Aⁱ	0.84 (3)	2.13 (2)	2.940 (2)	162 (2)
N2A—H2A⋯S1Aⁱ	0.86 (2)	2.51 (2)	3.3530 (15)	170 (2)

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Symmetry code: (i) Inline graphic .

Acknowledgments

The authors acknowledge financial support from the Brazilian agency CNPq. OE-H 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 (Aly et al., 2007). Aroylthioureas have also attracted much attention because of their unique properties, such as the strong coordination ability (Su et al., 2006). The title compound (I), Fig. 1, was synthesized from furoyl isothiocyanate and 2-aminopyridine in dry acetone. Studies of a number of substituted thioureas, including N-furoylthioureas, show intramolecular hydrogen bonding between N'H and the furoyl oxygen (Duque et al., 2008; Theodoro et al., 2008; Corrêa et al., 2008). There is also an intermolecular NH hydrogen bond with a sulfur of a neighboring molecule to form a two-dimensional network in these latter thioureas. The molecule structure of the title compound is shown in Figure 1. This thiourea derivative, like other pyridyl thioureas, is found in a conformation resulting from intramolecular hydrogen bonding of N2H(N'H) to the pyridine nitrogen, N3, and cis-cis like N-phenyl- N'-(2-pyridyl)thiourea derivatives (Valdés-Martínez et al., 2002). 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 1.667 (2) Å. The furan carbonyl (O1—C1—C3—O2 and O1a—C1a—C3a—O2a, two unique molecules) groups are inclined at an angle of -3.3 (3) ° and 0.6 (3) ° with respect to the plane formed by the thiourea moiety, whereas the 2-pyridyl (C7—C8—C9—C10—C11 and C7a—C8a—C9a—C10a—C11a, two unique molecules) rings are inclined at an angle of -3.3 (3) ° and 0.6 (3) °, respectively. In addition, the dihedral angles of two independent molecules between the furoyl groups and pyridine ring planes are 85.1 (2)° and 82.96 (8) °, respectively. The trans-cis geometry in the thiourea moiety is stabilized by the N1—H1···N3 intramolecular hydrogen bond. Another weaker bifurcated intramolecular hydrogen interaction between the furan oxygen atom O2 and the N1—H1 hydrogen atom is observed. The crystal structure is very interesting, stabilized by intermolecular bifurcated N—H···S (non bonding distance of 3.353 (2) Å and bond angle of 170 (2)°) and N—H···O (non bonding distance of 2.940 (2) Å and bond angle of 162 (2)°) hydrogen bonds forming centrosymmetric tetramers extending along the b axis.

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 2-aminopyridine. The resulting solid product was crystallized from ethanol yielding X-ray quality single crystals (m.p 150–151 °C). Elemental analysis (%) for C₁₁H₉N₃O₂S calculated: C 53.44, H 3.64, N 17.00, S 12.96; found: C 53.50, H 3.46, N 16.99, S 12.58.