3-Methyl-4-{(E)-[4-(methyl­sulfan­yl)benzyl­idene]amino}-1H-1,2,4-triazole-5(4H)-thione

B K Sarojini; P S Manjula; Gurumurthy Hegde; Dalbir Kour; Vivek K Gupta; Rajni Kant

doi:10.1107/S1600536813009690

. 2013 Apr 13;69(Pt 5):o718–o719. doi: 10.1107/S1600536813009690

3-Methyl-4-{(E)-[4-(methylsulfanyl)benzylidene]amino}-1H-1,2,4-triazole-5(4H)-thione

B K Sarojini ^a, P S Manjula ^a, Gurumurthy Hegde ^b, Dalbir Kour ^c, Vivek K Gupta ^c, Rajni Kant ^c,^*

PMCID: PMC3648251 PMID: 23723871

Abstract

In the title molecule, C₁₁H₁₂N₄S₂, the dihedral angle between the triazole and benzene rings is 21.31 (5)°. A weak intramolecular C—H⋯S hydrogen bond generates an S(6) ring motif. In the crystal, pairs of N—H⋯S hydrogen bonds form inversion dimers. In addition, π–π interactions are observed between the benzene rings, with a centroid–centroid separation of 3.7599 (11) Å.

Related literature

For background to Schiff base compounds, see: Dubey & Vaid (1991 ▶); Yadav et al. (1994 ▶); Galic et al. (2001 ▶). For biological applications of sulfur- and nitrogen-containing compounds, see: Wei et al. (1981 ▶, 1982 ▶); Thieme et al. (1973a ▶,b ▶); Dornow et al. (1964 ▶); Barrera et al. (1985 ▶); Malik et al., (2011 ▶). For related structures, see: Devarajegowda et al. (2012 ▶); Fun et al. (2008 ▶); Wang et al. (2008 ▶). For standard bond-length data, see: Allen et al. (1987 ▶). For hydrogen-bond graph-set motifs, see: Bernstein et al.(1995 ▶). graphic file with name e-69-0o718-scheme1.jpg

Experimental

Crystal data

C₁₁H₁₂N₄S₂
M _r = 264.37
Triclinic,
a = 7.7873 (2) Å
b = 9.5982 (2) Å
c = 9.6041 (2) Å
α = 76.608 (2)°
β = 70.602 (2)°
γ = 68.570 (2)°
V = 625.30 (2) Å³
Z = 2
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 293 K
0.3 × 0.2 × 0.1 mm

Data collection

Oxford Diffraction Xcalibur Sapphire3 diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.866, T _max = 1.000
30316 measured reflections
2449 independent reflections
2121 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.088
S = 1.03
2449 reflections
156 parameters
H-atom parameters constrained
Δρ_max = 0.26 e Å⁻³
Δρ_min = −0.17 e Å⁻³

Data collection: CrysAlis PRO (Oxford Diffraction, 2010 ▶); 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: ORTEP-3 for Windows (Farrugia, 2012 ▶) and PLATON (Spek, 2009 ▶); software used to prepare material for publication: PLATON.

Supplementary Material

Click here for additional data file.^{(20.9KB, cif)}

Crystal structure: contains datablock(s) I, global. DOI: 10.1107/S1600536813009690/lh5604sup1.cif

e-69-0o718-sup1.cif^{(20.9KB, cif)}

Click here for additional data file.^{(117.9KB, hkl)}

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536813009690/lh5604Isup2.hkl

e-69-0o718-Isup2.hkl^{(117.9KB, hkl)}

Click here for additional data file.^{(4.9KB, cml)}

Supplementary material file. DOI: 10.1107/S1600536813009690/lh5604Isup3.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
C8—H8⋯S1	0.93	2.57	3.212 (2)	126
N2—H2⋯S1ⁱ	0.86	2.48	3.328 (2)	169

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Symmetry code: (i) Inline graphic .

Acknowledgments

RK acknowledges the Department of Science & Technology for the sanction of the single-crystal X-ray diffractometer as a National Facility under mega research project No. SR/S2/ CMP-47/2003.

supplementary crystallographic information

Comment

During the last few decades, there has been a considerable interest in the chemistry of Schiff base compounds (Dubey & Vaid, 1991; Yadav et al.,1994). Schiff bases, containing different donor atoms, also find use in analytical applications and metal coordination (Galic et al., 2001). Since many compounds containing sulfur and nitrogen atoms are antihypertensive (Wei et al., 1981, 1982), analgesic (Thieme et al., 1973a,b), anti-inflammatory (Dornow et al., 1964), sedative (Barrera et al., 1985), or fungicidal (Malik et al., 2011), synthesis of the corresponding heterocyclic compounds could be of interest from the viewpoint of chemical reactivity and biological activity.

In the title compound (Fig. 1), the bond lengths and angles have values in the normal ranges (Allen et al., 1987) and are comparable with closely related structures (Devarajegowda et al., 2012; Fun et al., 2008; Wang et al., 2008). The dihedral angle between the triazole ring (N1/N2/C3/N4/C5) and the benzene ring (C9—C14) is 21.31 (5)°. The molecule exists in the thione tautomeric form, with an S═C distance of 1.681 (3) Å, which indicates substantial double-bond character for this bond [1.671 (24) Å](Allen et al., 1987). The methylidene amino linkage (N7/C8) is slightly twisted from the mean plane of the 1,2,4 triazole ring as indicated by the torsion angle C3–N4–N7–C8 of -30.8 (2)°. A weak intramolecular C—H···S hydrogen bond generates an S(6) ring motif (Bernstein et al.,1995). The packing of molecules within the unit cell is shown in Fig. 2. In the crystal, pairs of N—H···S hydrogen bonds form inversion dimers. In addition, π–π interactions are observed between the benzene rings with Cg···Cg(-x,-y,1-z) = 3.7599 (11) Å, where Cg is the centroid of the C9—C14 ring.

Experimental

To a suspension of 4-(methylthio)benzaldehyde (1.52 g, 0.01 mol) in methanol (15 ml), 4-amino-5-methyl-2,4-dihydro-3H-1,2,4-triazole-3-thione (0.01 mol, 1.65 g) was added and heated to form a clear solution. To this a few drops of conc.H₂SO₄ was added as a catalyst and refluxed for 5 h on a water bath. The precipitate formed was filtered and recrystallized from mixture of methanol and dioxane (2:1) to yield the titled compound. The single crystals were grown from a solution of the titlr compound of methanol (mp. 355–357 K).