N-(1,3-Thia­zol-2-yl)-N′-[(thio­phen-2-yl)carbon­yl]thio­urea hemihydrate

Durga Prasad Singh; Seema Pratap; Sema Öztürk Yildirim; Ray J Butcher

doi:10.1107/S160053681204500X

. 2012 Nov 7;68(Pt 12):o3295. doi: 10.1107/S160053681204500X

N-(1,3-Thiazol-2-yl)-N′-[(thiophen-2-yl)carbonyl]thiourea hemihydrate

Durga Prasad Singh ^a, Seema Pratap ^a, Sema Öztürk Yildirim ^b, Ray J Butcher ^c,^*

PMCID: PMC3588839 PMID: 23468804

Abstract

The title compound, C₉H₇N₃OS₃·0.5H₂O, crystallizes with two independent but similar molecules in the asymmetric unit, both of which are linked by a water molecule through O—H⋯N hydrogen bonds. In addition the water O atom is further linked by N—H⋯O hydrogen bonds to two additional main molecules, forming a tetrameric unit. These tetrameric units then form infinite ribbons parallel to the ac plane.The dihedral angle between the thiophenoyl and thiazolyl rings is 12.15 (10) and 21.69 (11)° in molecules A and B, respectively. The central thiourea core makes dihedral angles of 5.77 (11) and 8.61 (9)°, respectively, with the thiophenoyl and thiazolyl rings in molecule A and 8.41 (10) and 13.43 (12)° in molecule B. Each molecule adopts a trans–cis geometry with respect to the position of thiophenoyl and thiazole groups relative to the S atom across the thiourea C—N bonds. This geometry is stabilized by intramolecular N—H⋯O hydrogen bonds.

Related literature

For general background to aroylthiourea and its derivatives, see: Aly et al. (2007 ▶). For related structures, see: Koch (2001 ▶); Pérez et al. (2008 ▶). For their biological activity, see: Saeed et al. (2008 ▶); Gu et al. (2007 ▶); Xu et al. (2004 ▶); Yan & Xue (2008 ▶). graphic file with name e-68-o3295-scheme1.jpg

Experimental

Crystal data

C₉H₇N₃OS₃·0.5H₂O
M _r = 278.37
Triclinic,
a = 7.4489 (4) Å
b = 11.1060 (6) Å
c = 14.7935 (7) Å
α = 93.559 (4)°
β = 99.813 (4)°
γ = 107.789 (5)°
V = 1139.74 (11) Å³
Z = 4
Cu Kα radiation
μ = 5.86 mm⁻¹
T = 123 K
0.35 × 0.25 × 0.18 mm

Data collection

Oxford Diffraction Xcalibur (Ruby, Gemini CCD) diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Agilent, 2011 ▶) T _min = 0.441, T _max = 1.000
7828 measured reflections
4566 independent reflections
3906 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.039
wR(F ²) = 0.110
S = 1.08
4566 reflections
304 parameters
3 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.43 e Å⁻³
Δρ_min = −0.30 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.^{(21.5KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S160053681204500X/zs2240sup1.cif

e-68-o3295-sup1.cif^{(21.5KB, cif)}

Click here for additional data file.^{(223.7KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S160053681204500X/zs2240Isup2.hkl

e-68-o3295-Isup2.hkl^{(223.7KB, hkl)}

Click here for additional data file.^{(4.5KB, cml)}

Supplementary material file. DOI: 10.1107/S160053681204500X/zs2240Isup3.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
N1A—H1AA⋯O1W ⁱ	0.86	2.22	3.003 (3)	152
N1B—H1BA⋯O1W ⁱⁱ	0.86	2.14	2.973 (3)	163
N2A—H2AA⋯O1A	0.86	1.89	2.599 (3)	138
N2B—H2BA⋯O1B	0.86	1.90	2.588 (3)	136
O1W—H1W⋯N3B	0.82 (1)	2.06 (1)	2.852 (3)	163 (4)
O1W—H2W⋯N3A	0.82 (1)	2.09 (1)	2.892 (3)	167 (3)

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

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.

supplementary crystallographic information

Comment

Aroylthiourea and its derivatives are an important class of organic compounds in which the sulphur atom is a major ligand atom and plays an important role in coordination chemistry with transition metals. These compounds are found to be useful in heterocyclic synthesis and many of these substrates have interesting biological activities (Aly et al., 2007). Aroylthioureas and and its derivatives are also known to exhibit a wide range of biological activities, such as anticancer (Saeed et al., 2010), anti-fungal (Saeed et al., 2008), antibacterial, antiviral, anti-tubercular, insecticidal, organocatalyst (Gu et al., 2007) and as agrochemicals (Xu et al., 2004).

The title compound (Fig. 1), C₉H₇N₃OS₃.0.5H₂O, crystallizes with two independent but similar molecules in the asymmetric unit both of which are linked by a water molecule through O—H···N hydrogen bonds. In addition the water O is further linked by N-H···O hydrogen bonds to two additional C₉H₇N₃OS₃ molecules, forming a tetrameric moiety. These tetrameric moieties then form infinite ribbons parallel to the ac plane (Fig.2).

The main bond lengths and angles are within the range obtained for similar compounds (Koch et al., 2001; Perez et al., 2008). The C6A-S2A [1.657 (2)Å], C6B-S2B [1.659 (2)Å] and C5A-O1A [1.233 (3)Å], C5B-O1B [1.232 (3)Å] bonds show typical double-bond character. However, the C-N bond lengths, C5A-N1A [1.388 (3)Å], C6A-N1A [1.395 (3)Å], C6A-N2A [1.345 (3)Å], C7A-N2A [1.383 (3)Å] and C5B-N1B [1.385 (3)Å], C6B-N1B [1.390 (3)Å], C6B-N2B [1.350 (3)Å], C7B-N2B [1.383 (3)Å] are shorter than the normal C-N single-bond length of about 1.48 Å (Allen, 2002). These results can be explained by the existence of resonance in this part of the molecule. In first molecule(A) the central thiourea fragment (N1A-C6A-S2A-N2A) makes the dihedral angle of 5.77(0.11)° and 8.61(0.09 )° with thiophenoyl (S1A/C4A-C1A) and thiazolyl ring (C7A-S3A-C9A-C8A-N3A). Where as in second molecule(B) the central thiourea fragment (N1B/C6B/S2B/N2B) makes the dihedral angle of 8.41(0.10)° with (S1B/C4B-C1B) group, and the thiazole ring (C7B-S3B-C9B-C8B-N3B) is 13.43(0.12)°, respectively. The dihedral angle between the thiophenoyl and thiazolyl rings is 12.15(0.10)° in molecule A and 21.69(0.11)° in molecule B. The trans-cis geometry in the thiourea moiety of both molecule is stabilized by the N-H···O and C-H···O hydrogen bonds (Fig.2 and Table 1).

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 product was recrystallized from ethanol as colorless block crystals.