4-Ethyl-3-(2-thienylmeth­yl)-Δ2-1,2,4-triazoline-5-thione

Monika Wujec; Liliana Mazur; Zofia Rzączyńska

doi:10.1107/S1600536809000440

. 2009 Jan 10;65(Pt 2):o274. doi: 10.1107/S1600536809000440

4-Ethyl-3-(2-thienylmethyl)-Δ²-1,2,4-triazoline-5-thione

Monika Wujec ^a, Liliana Mazur ^b,^*, Zofia Rzączyńska ^b

PMCID: PMC2968376 PMID: 21581888

Abstract

The title compound, C₉H₁₁N₃S₂, exists in the thione form in the crystal structure. The central triazole ring is almost perpendicular to the thiophene ring which is disordered over two orientations [dihedral angles of 88.5 (7) and 85.7 (8)° for the two orientations]. The crystal structure is stabilized by strong intermolecular N—H⋯S hydrogen bonds, forming centrosymmetric dimers, and by some weak C—H⋯S interactions.

Related literature

For background on the applications of 1,2,4-triazole and its derivatives, see: Ünver et al. (2006 ▶); Dobosz et al. (2002 ▶); Jian et al. (2005 ▶); Maliszewska-Guz et al. (2005 ▶); Al-Soud et al. (2004 ▶); Amir & Shikha (2004 ▶); Collin et al. (2003 ▶); Demirayak et al. (2000 ▶); Palaska et al. (2002 ▶); Shivarama et al. (2006 ▶). For details of the synthesis, see: Wujec et al. (2004 ▶, 2007 ▶). For related structures, see: Yilmaz et al. (2005 ▶).

Experimental

Crystal data

C₉H₁₁N₃S₂
M _r = 225.33
Monoclinic,
a = 6.813 (1) Å
b = 17.119 (2) Å
c = 9.846 (1) Å
β = 100.88 (1)°
V = 1127.7 (2) Å³
Z = 4
Mo Kα radiation
μ = 0.44 mm⁻¹
T = 295 (2) K
0.47 × 0.30 × 0.16 mm

Data collection

Oxford Diffraction Xcalibur diffractometer
Absorption correction: none
2735 measured reflections
2592 independent reflections
1130 reflections with I > 2σ(I)
R _int = 0.026

Refinement

R[F ² > 2σ(F ²)] = 0.052
wR(F ²) = 0.111
S = 0.98
2592 reflections
147 parameters
H-atom parameters constrained
Δρ_max = 0.16 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: CrysAlis CCD (Oxford Diffraction, 2005 ▶); cell refinement: CrysAlis RED (Oxford Diffraction, 2005 ▶); data reduction: CrysAlis RED; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXL97 and enCIFer (Allen et al., 2004 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536809000440/at2696sup1.cif

e-65-0o274-sup1.cif^{(17.4KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809000440/at2696Isup2.hkl

e-65-0o274-Isup2.hkl^{(127.3KB, 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⋯S1ⁱ	0.86	2.44	3.287 (3)	169
C6—H6a⋯S1ⁱⁱ	0.97	2.99	3.949 (4)	172
C9—H9⋯S1ⁱⁱⁱ	0.93	2.97	3.659 (4)	132
C8′—H8′⋯S2^iv	0.93	3.02	3.928 (7)	166

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

supplementary crystallographic information

Comment

1,2,4-Triazole and its derivatives represent one of the most biologically active classes of compounds possessing a wide spectrum of activities, such as antimicrobial, fungicidal, anti-inflammatory, antiviral, antitumor or analgesic activity (Al-Soud et al., 2004; Amir & Shikha, 2004; Collin et al., 2003; Demirayak et al., 2000; Maliszewska-Guz et al., 2005; Palaska et al., 2002; Shivarama et al., 2006; Wujec et al. 2007). The 1,2,4-triazole nucleus has been incorporated into a wide variety of therapeutically important drugs e.g. Fluconazole, Itraconazole, Anastrazole, Ribavirin. In recent years 1,2,4-triazole finds an important place in medicinal chemistry as material for the preparation of antibacterial agents (Demirayak et al., 2000). In this context, we described the synthesis and antibacterial activity of a series of 1,2,4-triazoline-5-thione derivatives (Wujec et al. 2004). In the present paper we report the structure of one of them: 4-ethyl-3-(thiophene-2-yl-methyl)-Δ²-1,2,4-triazoline-5-thione (I). This compound inhibite the growth of Trichophyton spp.

In the title compound (Fig. 1), the C5—S1 bond length [1.673 (2) Å] is within the values observed for a C=S double bond. In the planar 1,2,4-triazole ring the C3=N2 bond is clearly double, being much shorter then the other C—N bonds. This distance is also comparable to literature data (Yilmaz et al., 2005). The thiophene ring is disordered over two orientatians with respect to the C6—C7 bond; the dihedral angles between the triazole and the thiophene rings for the two orientations of the second one are 88.5 (7) and 85.7 (8)°. Atoms C6 and C11 lie in the plane of triazole, whereas the ethyl atom C12 is signifficantly displaced from the plane of central system as indicate from the torsion angle C5—N4—C11—C12, being of 83.3 (3)°.

The crystal structure is stabilized by strong intermolecular N1—H1···S1 hydrogen bonds, forming centrosymmetric dimers (Fig. 2), together with some weak C—H···S interactions (Table 1).

Experimental

4-Ethyl-3-(thiophene-2-yl-methyl)-Δ²-1,2,4-triazoline-5-thione was synthesized according to the method which was described in a previous paper (Wujec et al., 2004). Prism-shaped colourless single crystals, suitable for X-ray diffraction measurements, were obtained by the slow evaporation of a 2-propanol solution of the compound.