(E)-5-[(2-Hy­droxy-5-meth­oxy­benzyl­idene)amino]-1,3,4-thia­diazole-2(3H)-thione

Hadi Kargar; Reza Kia; Muhammad Nawaz Tahir

doi:10.1107/S1600536811047362

. 2011 Nov 16;67(Pt 12):o3311. doi: 10.1107/S1600536811047362

(E)-5-[(2-Hydroxy-5-methoxybenzylidene)amino]-1,3,4-thiadiazole-2(3H)-thione

Hadi Kargar ^a,^*, Reza Kia ^b,^c, Muhammad Nawaz Tahir ^d,^*

PMCID: PMC3238963 PMID: 22199812

Abstract

In the title thione–Schiff base compound, C₁₀H₉N₃O₂S₂, the dihedral angle between the benzene ring and the five-membered ring is 6.69 (8)°. An intramolecular O—H⋯N hydrogen bond forms an S ₂ ²(6) ring. In the crystal, inversion dimers linked by pairs of N—H⋯S interactions occur, generating R ₂ ²(8) ring motifs. The crystal structure features a S⋯S contact [3.3776 (7) Å], which is significantly shorter than the sum of the van der Waals radii (3.7 Å). The crystal structure also features C—H⋯O and π–π interactions [centroid–centroid distances = 3.4636 (9)–3.808 (1) Å].

Related literature

For standard values of bond lengths, see: Allen et al. (1987 ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶). For the biological versatility of thione ligands see, for example: Kumar et al. (1988 ▶); Yadav et al. (1989 ▶). For a related structure, see: Zhang (2003 ▶). For van der Waals radii, see: Bondi, (1964 ▶).

Experimental

Crystal data

C₁₀H₉N₃O₂S₂
M _r = 267.32
Triclinic,
a = 6.2266 (2) Å
b = 8.0680 (2) Å
c = 11.9695 (3) Å
α = 83.027 (2)°
β = 77.993 (1)°
γ = 87.898 (1)°
V = 583.76 (3) Å³
Z = 2
Mo Kα radiation
μ = 0.45 mm⁻¹
T = 291 K
0.11 × 0.08 × 0.05 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.952, T _max = 0.978
10303 measured reflections
2894 independent reflections
1990 reflections with I > 2σ(I)
R _int = 0.030

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.102
S = 1.02
2894 reflections
155 parameters
H-atom parameters constrained
Δρ_max = 0.30 e Å⁻³
Δρ_min = −0.25 e Å⁻³

Data collection: APEX2 (Bruker, 2005 ▶); cell refinement: SAINT (Bruker, 2005 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL; software used to prepare material for publication: SHELXTL and PLATON (Spek, 2009 ▶).

Supplementary Material

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811047362/ff2041sup1.cif

e-67-o3311-sup1.cif^{(16.4KB, cif)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811047362/ff2041Isup2.hkl

e-67-o3311-Isup2.hkl^{(142KB, hkl)}

Supplementary material file. DOI: 10.1107/S1600536811047362/ff2041Isup3.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
O1—H1⋯N1	0.85	1.84	2.616 (2)	151
N3—H3⋯S2ⁱ	0.80	2.53	3.3163 (15)	169
C2—H2A⋯O1ⁱⁱ	0.93	2.57	3.481 (2)	167
C3—H3A⋯O2ⁱⁱⁱ	0.93	2.52	3.442 (3)	172

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

Acknowledgments

HK thanks PNU for financial support. RK thanks the Islamic Azad University. MNT thanks GC University of Sargodha, Pakistan, for the research facility.

supplementary crystallographic information

Comment

Compounds incorporating a thiadiazole ring have attracted much attention due to their biological activity (Kumar et al., 1988; Yadav et al., 1989). Here we report the crystal structure of a new Schiff base compound containing a thiadiazol ring system.

The asymmetric unit of the title compound, Fig. 1, comprises a thione-Schiff base ligand. The bond lengths (Allen et al., 1987) and angles are within the normal ranges and are comparable to the related structure (Zhang, 2003).

The dihedral angle between the benzene ring and the five-membered ring is 6.69 (8)°. An intramolecular O—H···N hydrogen bond makes S₂²(6) ring motif. Intermolecular N—H···S interactions link neighboring molecules into individual dimers with R₂²(8) ring motifs (Bernstein et al.,1995). The interesting feature of the crystal structure is a short S(1)···S(1)ⁱ [3.3776 (7)Å; (i) 1 - x,1 - y,1 - z ] contact which is significantly shorter than the sum of the Van der Waals radius of S atoms (Bondi, 1964). The crystal structure is stabilized by the intermolecular C—H···O, and π-π interactions [Cg1···Cg1^iv = 3.4636 (9)Å, (iv) -1 - x, -y, 1 -z; Cg1···Cg2^v = 3.5242 (10)Å, (v) 1 + x, y, z; Cg2···Cg2^vi = 3.808 (1)Å, (vi) -x, 1 - y, -z Cg1 and Cg2 are centroids of S(1)/C(8)/N(2)/N(3)/C(9) and C1–C6 rings, respectively.

Experimental

The title compound was synthesized by adding 5-methoxy-salicylaldehyde (1 mmol) to a solution of 5-aminothiophene-2-thiol (1 mmol) in ethanol (30 ml). The mixture was refluxed with stirring for half an hour. The resultant solution was filtered. Yellow single crystals of the title compound suitable for X-ray structure determination were recrystallized from ethanol by slow evaporation of the solvents at room temperature over several days.