3-[(Furan-2-yl)carbon­yl]-1-(pyrimi­din-2-yl)thio­urea

Durga P Singh; Seema Pratap; Sushil K Gupta; Ray J Butcher

doi:10.1107/S1600536812044029

. 2012 Nov 7;68(Pt 12):o3300–o3301. doi: 10.1107/S1600536812044029

3-[(Furan-2-yl)carbonyl]-1-(pyrimidin-2-yl)thiourea

Durga P Singh ^a, Seema Pratap ^a, Sushil K Gupta ^b, Ray J Butcher ^c,^*

PMCID: PMC3588843 PMID: 23468808

Abstract

The title compound, C₁₀H₈N₄O₂S, was synthesized from furoyl isothiocynate and 2-aminopyrimidine in dry acetone. The two N—H groups are in an anti conformation with respect to each other and one N—H group is anti to the C=S group while the other is syn. The amide C=S and the C=O groups are syn to each other. The mean plane of the central thiourea fragment forms dihedral angles of 13.50 (14) and 5.03 (11)° with the furan and pyrimidine rings, respectively. The dihedral angle between the furan and pyrimidine rings is 18.43 (10)°. The molecular conformation is stabilized by an intramolecular N—H⋯N hydrogen bond generating an S(6) ring motif. In the crystal, molecules are linked by pairs of N—H⋯N and weak C—H⋯S hydrogen bonds to form inversion dimers.

Related literature

For a general background to the biological activity of thiourea, see: Koketsu & Ishihara (2006 ▶). For heterocyclic derivatives, metal complexes and molecular electronics, see: Zeng et al. (2003 ▶); D’hooghe et al. (2005 ▶); Aly et al. (2007 ▶); Duque et al. (2009 ▶). For related structures, see: Singh et al. (2012 ▶); Koch (2001 ▶); Hassan et al. (2007 ▶); Pérez et al. (2008 ▶); Yan & Xue (2008 ▶).

Experimental

Crystal data

C₁₀H₈N₄O₂S
M _r = 248.26
Monoclinic,
a = 5.6962 (2) Å
b = 21.0530 (7) Å
c = 8.7901 (3) Å
β = 95.559 (3)°
V = 1049.17 (6) Å³
Z = 4
Cu Kα radiation
μ = 2.74 mm⁻¹
T = 123 K
0.40 × 0.22 × 0.11 mm

Data collection

Agilent Xcalibur (Ruby, Gemini) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.421, T _max = 1.000
6957 measured reflections
2028 independent reflections
1951 reflections with I > 2σ(I)
R _int = 0.028

Refinement

R[F ² > 2σ(F ²)] = 0.038
wR(F ²) = 0.108
S = 1.04
2028 reflections
154 parameters
H-atom parameters constrained
Δρ_max = 0.46 e Å⁻³
Δρ_min = −0.21 e Å⁻³

Data collection: CrysAlis PRO (Agilent, 2011 ▶); cell refinement: CrysAlis PRO; data reduction: CrysAlis PRO; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Click here for additional data file.^{(21.2KB, cif)}

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812044029/lh5548sup1.cif

e-68-o3300-sup1.cif^{(21.2KB, cif)}

Click here for additional data file.^{(99.8KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812044029/lh5548Isup2.hkl

e-68-o3300-Isup2.hkl^{(99.8KB, hkl)}

Click here for additional data file.^{(4.4KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536812044029/lh5548Isup3.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
N1—H1B⋯N3	0.86	1.89	2.6240 (18)	142
N2—H2B⋯N4ⁱ	0.86	2.21	3.0726 (19)	175
C10—H10A⋯S1ⁱ	0.93	2.76	3.5536 (17)	144

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Symmetry code: (i) Inline graphic .

Acknowledgments

DPS and SP are grateful to Banaras Hindu University, Varanasi, for financial support. RJB acknowledges the NSF–MRI program (grant No. CHE0619278) for funds to purchase the X-ray diffractometer. SKG wishes to acknowledge the USIEF for the award of a Fulbright–Nehru Senior Research Fellowship.

supplementary crystallographic information

Comment

Thiourea and its derivatives are known to exhibit a wide variety of biological activities (Koketsu & Ishihara, 2006). These are also widely used as precursors or intermediates towards the syntheisis of a variety of heterocyclic compounds (Zeng et al., 2003; D'hooghe, et al., 2005). In addition, aroylthioureas have applications in metal complexes and molecular electronics (Aly et al., 2007; Duque et al., 2009). The structure of a related compound was recently published (Yan & Xue, 2008) in which the molecule showed excellent herbicidal activity.

In view of the biological importance of thiourea and its furoic acid derviatives, the structure of the title compound was determined. In the title compound (Fig. 1), the conformation of the two N—H bonds are anti to each other, and one of them is anti to the C═S and the other is syn in the urea moiety. Furthermore, the amide C═S and the C═O groups are syn to each other, similar to the syn conformation observed in 1-furoyl-3-methyl-3-phenylthiourea (Pérez et al., 2008) and in N-(2-furoyl)-N^'(6-methyl-2-pyridyl)thiourea (Hassan et al., 2007). The bond lengths and angles in the title compound are comparable to other thiourea derivatives (Koch 2001; Pérez et al., 2008; Singh et al., 2012). The C6—S1 and C5—O2 bonds show typical double-bond character. However, the C—N bond lengths, C5—N1, C6—N1, C6—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 (O2/C5/N1/C6/N2) makes dihedral angle of 13.50 (14)° with furan ring (O1/C1/C2/C3/C4)and 5.03 (11)° with pyrimidine ring (C7/N3/C8/C9/C10/N4), respectively. The dihedral angle between the mean planes of the furan and pyrimidine rings is 18.43 (10)°. The moleculer geometry is stabilized by an intramolecular N—H···N hydrogen bond generating an S(6) ring motif. In the crystal, molecules are linked by pairs of N—H···N and weak C—H···S hydrogen bonds (Table 1) forming centrosymmetric dimers (Fig. 2).

Experimental

A solution of 2-thiophenecarbonyl chloride (0.01 mol) in anhydrous acetone (80 ml) was added dropwise to a suspension of ammonium thiocyanate (0.01 mol) in anhydrous acetone (50 ml) and the reaction mixture was refluxed for 50 minutes. After cooling to room temperature, a solution of 4-chloroaniline (0.01 mol) in dry acetone (25 ml) was added and the resulting mixture refluxed for 2 h. The reaction mixture was poured into five times its volume of cold water, upon which the thiourea precipitated. The resulting solide product was crystallized from acetone yielding yellow colour X-ray quality single crystals. Yield: 80%; M.P.: 455 - 456 K). Anal. Calc. for C₁₀H₈N₄O₂S (%): C, 48.38; H,3.25; N, 22.57. Found: C, 48.49; H, 3.28; N, 22.50.