1-(Naphthalen-1-yl)-3-[(thio­phen-2-yl)carbon­yl]thio­urea

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

doi:10.1107/S1600536812035350

. 2012 Sep 8;68(Pt 10):o2882–o2883. doi: 10.1107/S1600536812035350

1-(Naphthalen-1-yl)-3-[(thiophen-2-yl)carbonyl]thiourea

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

PMCID: PMC3470236 PMID: 23125680

Abstract

In the title compound, C₁₆H₁₂N₂OS₂, the dihedral angles between the mean planes of the central thiourea core and the thiophene ring and the naphthalene ring system are 1.8 (2) and 6.45 (18)°, respectively. The molecule adopts a trans–cis conformation with respect to the position of thiophenoyl and naphthyl groups relative to the S atom across the thiourea C—N bonds. Both the thiophene ring and the sulfanylidene S atom are disordered over two sets of sites with occupancies of 0.862 (3):0.138 (3) and 0.977 (3):0.023 (3), respectively. An intramolecular N—H⋯O hydrogen bond is observed. The crystal packing features two N—H⋯S hydrogen bonds.

Related literature

For heterocyclic thiourea derivatives, metal complexes and their applications, see: D’hooghe et al. (2005 ▶); Aly et al. (2007 ▶); Estévez-Hernández et al. (2007 ▶); Saeed et al. (2008a ▶,b ▶,c ▶). For related structures, see: Singh et al. (2012 ▶); Koch (2001 ▶); Pérez et al. (2008 ▶). For the synthesis, see: Otazo-Sánchez et al. (2001 ▶).

Experimental

Crystal data

C₁₆H₁₂N₂OS₂
M _r = 312.40
Monoclinic,
a = 14.929 (2) Å
b = 5.9086 (8) Å
c = 17.071 (3) Å
β = 104.030 (14)°
V = 1460.9 (4) Å³
Z = 4
Mo Kα radiation
μ = 0.36 mm⁻¹
T = 173 K
0.35 × 0.25 × 0.15 mm

Data collection

Oxford Diffraction Xcalibur Eos diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2007 ▶) T _min = 0.712, T _max = 1.000
4822 measured reflections
2625 independent reflections
1626 reflections with I > 2σ(I)
R _int = 0.052

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.165
S = 1.09
2625 reflections
210 parameters
10 restraints
H-atom parameters constrained
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.31 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2007 ▶); 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

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536812035350/bq2371sup1.cif

e-68-o2882-sup1.cif^{(20.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536812035350/bq2371Isup2.hkl

e-68-o2882-Isup2.hkl^{(126.3KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536812035350/bq2371Isup3.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—H1A⋯O1	0.88	1.86	2.615 (3)	143
N2—H2A⋯S2B	0.88	2.57	3.026 (14)	113
N2—H2A⋯S1A ⁱ	0.88	2.56	3.41 (4)	164
N2—H2A⋯S1B ⁱ	0.88	2.80	3.557 (3)	145

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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

Aroylythiourea and its derivatives are an important class of organic compounds due to their ability to form a variety of heterocyclic compounds (D'hooghe et al., 2005) and metal complexes that can be used as ionophores in potentiometric and amperometric sensors (Aly et al., 2007; Estévez-Hernández et al., 2007) and as epoxy resin curing agents and accelerators (Saeed et al., 2008a, 2008b, 2008c). The title compound, N-(naphthalen-1-yl)-3-oxo-3-(thiophen-2-yl)propanethioamide is an important precursor with O and S as potential donor sites, and can be used to form heterocycles and metal complexes. We have reported recently the synthesis and crystal structure of methyl 2-(thiophene-2-carboxamido)benzoate (Singh et al., 2012). We herein report the synthesis and crystal structure of the biologically active title compound.

In the title compound (Fig.1) the bond lengths and angles are within the ranges observed for similar compounds (Koch, 2001; Pérez et al., 2008). The C11—S1B [1.661 (3) Å] and C12—O1 [1.230 (3) Å] bonds show typical double-bond character. However, the C—N bond lengths, C12—N2 [1.376 (4) Å], C11—N1 [1.326 (4) Å], C11—N2 [1.397 (4) Å] and C1—N1 [1.419 (4) Å] are all shorter than the normal C—N single-bond length of about 1.48 Å and indicate some degree of delocalization. The central thiourea fragment (N1/C11/N2/C12/O1) makes a dihedral angle of 2.03 (41)° with the major part of the 2-thiophenoyl group (S2/C13/C14/C15/C16) and 6.51 (16)° with the naphthalene ring (C1/C2/C3/C4/C5/C6/C7/C8/C9/C10), respectively. Thus, the conformation is almost planar and adopts a trans-cis configuration with respect to the position of the thiophenoyl and naphthyl groups relative to the S atom across the thiourea C—N bonds. This geometry is stabilized by both an N1—H1···O1 intramolecular hydrogen bond and two intermolecular N—H···S hydrogen bonds (Fig.2). In addition, both the thiophene ring and the thio S are disordered over two positions with occupancies of 0.862 (3)/0.138 (3) and 0.977 (3)/0.023 (3), respectively.

Experimental

The title compound was synthesized according to a previous report (Otazo-Sánchez et al., 2001), by converting furoyl choride into furoyl isothiocyanate and then condensing with α-naphthylamine. The resulting solid product was crystallized from ethanol yielding X-ray quality single crystals (M.P.: 459 K). Anal. Calc. for C₁₆H₁₂N₂OS₂ (%): C, 61.51; H, 3.87; N, 8.97. Found: C, 61.20; H, 3.80; N, 9.10.