4-Amino-3-(o-tolyloxymethyl)-1H-1,2,4-triazole-5(4H)-thione

The asymmetric unit of the title compound, C10H12N4OS, contains two independent molecules, A and B, which differ significantly in the relative orientations of the benzene and triazole rings. The dihedral angle between the above two rings is 6.94 (5)° in molecule A and 77.60 (5)° in molecule B. In the crystal, molecules are linked into a three-dimensional network by N—H⋯S, N—H⋯O, N—H⋯N and C—H⋯S hydrogen bonds and π–π interactions between the benzene and triazole rings [centroid–centroid distance = 3.5311 (6) Å] are also present.

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 Comment 1,2,4-Triazole and its derivatives were reported to exhibit various pharmacological activities such as antimicrobial, analgesic, anticancer, anti-inflammatory and antioxidant properties (Amir et al., 2008;Kuş et al., 2008;Padmavathi et al., 2008;Sztanke et al., 2008). Some of the present day drugs such as ribavirin (antiviral agent), rizatriptan (antimigraine agent), alprazolam (anxiolytic agent), fluconazole and itraconazole (antifungal agents) are the best examples for potent molecules possessing triazole nucleus. The amino and mercapto groups of 1,2,4-triazoles serve as readily accessible nucleophilic centers for the preparation of N-bridged heterocycles. Keeping in view of this biological importance, the title compound was synthesized and its crystal structure is reported here.
In the title compound ( Fig. 1), the bond lengths (Allen et al., 1987) and angles are found to have normal values and are comparable to closely related structures (Fun et al., 2008a(Fun et al., ,b,2009. The dihedral angle between the triazole ring (N1A-N3A/ C1A/C2A) and the benzene ring (C4A-C9A) of molecule A is 6.94 (5)°, whereas the dihedral angle between the triazole ring (N1B-N3B/C1B/C2B) and the benzene ring (C4B-C9B) of molecule B is 77.60 (5)° indicating that for molecule B, these rings are significantly twisted from each other.

Experimental
O-Cressoyloxyacetyl hydrazine (18.0 g, 0.1 mol) was added slowly to a solution of potassium hydroxide (8.4 g, 0.15 mol) in ethanol (150 ml). The resulting mixture was stirred well till a clear solution was obtained. Carbon disulfide (11.4 g, 0.15 mol) was added drop-wise and the contents were stirred vigorously. Further stirring was continued for 24 h. The resulting mixture was diluted with 100 ml of ether and the precipitate formed was collected by filtration, washed with dry ether and dried at 65 °C under vacuum. It was used for the next step without any purification.
A mixture of potassium dithiocarbazinate (29.4 g, 0.1 mol), hydrazine hydrate (99%, 0.2 mol) and water (2 ml) was gently heated to boil for 30 minutes. Heating was continued until the evacuation of hydrogen sulfide ceases. The reaction mixture was cooled to room temperature, diluted with water (100 ml) and acidified with HCl. The solid mass that separated was collected by filtration, washed with water and dried. Recrystallization was done from ethanol. Yield: 13.7 g, 58.0%, m.p. 400-402 K (Eweiss et al., 1986).
supplementary materials sup-2 Refinement N-bound H atoms were located in a difference Fourier map and refined freely. C-bound H atoms were positioned geometrically [C-H = 0.93-0.97 Å] and refined using a riding model, with U iso (H) = 1.2U eq (C) and 1.5U eq (methyl C). A rotating group model was used for the methyl groups. Fig. 1. The asymmetric unit of the title compound, showing 50% probability displacement ellipsoids and the atom-numbering scheme.

Special details
Experimental. The crystal was placed in the cold stream of an Oxford Cyrosystems Cobra open-flow nitrogen cryostat (Cosier & Glazer, 1986) operating at 100.0 (1) K. Refinement. Refinement of F 2 against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F 2 , conventional R-factors R are based on F, with F set to zero for negative F 2 . The threshold expression of F 2 > σ(F 2 ) is used only for calculating Rfactors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F 2 are statistically about twice as large as those based on F, and R-factors based on ALL data will be even larger.