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

Hoong-Kun Fun; Jia Hao Goh; A M Vijesh; Mahesh Padaki; Arun M Isloor

doi:10.1107/S1600536809027664

. 2009 Jul 18;65(Pt 8):o1918–o1919. doi: 10.1107/S1600536809027664

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

Hoong-Kun Fun ^a,^*,^‡, Jia Hao Goh ^a, A M Vijesh ^b,^c,^§, Mahesh Padaki ^c, Arun M Isloor ^c

PMCID: PMC2977210 PMID: 21583604

Abstract

In the title triazole compound, C₁₀H₁₂N₄OS, the triazole ring is essentially planar [maximum deviation = 0.009 (1) Å] and forms a dihedral angle of 5.78 (4)° with the benzene ring. In the crystal structure, molecules are linked into dimers by centrosymmetric N—H⋯S interactions. These dimers are linked into two-molecule-wide tapes by N—H⋯N and S⋯S [3.2634 (3) Å] interactions. In addition, they are further interconnected by weak N—H⋯S interactions into sheets parallel to the ab plane. The crystal structure is further stabilized by weak intermolecular C—H⋯π interactions.

Related literature

For general background and applications of triazole derivatives, see: Amir et al. (2008 ▶); Kuş et al. (2008 ▶); Krzysztof et al. (2008 ▶); Padmavathi et al. (2008 ▶). For the preparation, see: Conti (1964 ▶). For related structures, see: Fun et al. (2008 ▶, 2009 ▶). For the stability of the temperature controller used for the data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₀H₁₂N₄OS
M _r = 236.30
Triclinic,
a = 5.9977 (1) Å
b = 6.4002 (1) Å
c = 15.5506 (2) Å
α = 89.352 (1)°
β = 83.157 (1)°
γ = 65.562 (1)°
V = 539.11 (1) Å³
Z = 2
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 100 K
0.47 × 0.30 × 0.09 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.878, T _max = 0.975
19910 measured reflections
4712 independent reflections
4228 reflections with I > 2σ(I)
R _int = 0.022

Refinement

R[F ² > 2σ(F ²)] = 0.032
wR(F ²) = 0.095
S = 1.05
4712 reflections
193 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.59 e Å⁻³
Δρ_min = −0.33 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 datablocks global, I. DOI: 10.1107/S1600536809027664/tk2497sup1.cif

e-65-o1918-sup1.cif^{(17.6KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809027664/tk2497Isup2.hkl

e-65-o1918-Isup2.hkl^{(230.8KB, 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
N2—H1N2⋯S1ⁱ	0.930 (13)	2.412 (13)	3.3364 (7)	172.5 (11)
N4—H1N4⋯N1ⁱⁱ	0.930 (17)	2.428 (17)	3.2100 (9)	141.6 (12)
N4—H2N4⋯S1ⁱⁱⁱ	0.894 (15)	2.937 (16)	3.5456 (7)	126.8 (12)
C10—H10C⋯Cg2^iv	0.968 (18)	2.697 (19)	3.6250 (9)	160.8 (14)

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Symmetry codes: (i) Inline graphic ; (ii) ; (iii) ; (iv) . Cg2 is the centroid of the C4–C9 ring.

Acknowledgments

HKF and JHG thank Universiti Sains Malaysia for the Research Universiti Golden Goose Grant (No. 1001/PFIZIK/811012). JHG thanks Universiti Sains Malaysia for the award of a Research Fellowship. AMI is thankful to the Head of the Department of Chemistry and the Director, NITK Surathkal, for providing research facilities.

supplementary crystallographic information

Comment

1,2,4-Triazole and its derivatives were reported to exhibit various pharmacological activities such as anti-microbial, analgesic, anti-inflammatory, anti-cancer and anti-oxidant properties (Amir et al., 2008; Kuş et al., 2008; Krzysztof et al., 2008; Padmavathi et al., 2008). Some of the present day drugs such as Ribavirin (anti-viral agent), Rizatriptan (anti-migraine agent), Alprazolam (anxiolytic agent), Fluconazole and Itraconazole (anti-fungal agents) are the best examples for potent molecules possessing the triazole nucleus. The amino and mercapto groups of thio-substituted 1,2,4-triazole serve as readily accessible nucleophilic centers for the preparation of N-bridged heterocycles. In view of their biological importance, we have synthesized the title compound (I) to study its crystal structure.

In (I), Fig. 1, the 1,2,4-triazole ring (C1/C2/N1-N3) is essentially planar, with a maximum deviation of 0.009 (1) Å for atom C1. The 1,2,4-triazole ring makes dihedral angle of 5.78 (4)° with the C4-C9 benzene ring. The bond lengths and angles in the molecule are comparable to those found in closely related structures (Fun et al., 2008, 2009).

In the crystal packing (Fig. 2), centrosymmetrically related molecules are linked into dimers by N2—H1N2···S1 interactions (Table 1). These dimers are linked into two-molecule-wide tapes by N4—H1N4···N1 (Table 1) and by short S1···S1 contacts of 3.2634 (3) Å; symmetry code: 2-x, -y, -z. In addition, these tapes are interconnected into sheets parallel to the ab plane by weak N4—H2N4···S1 interactions (Table 1). The crystal structure is further stabilized by weak C···H···π interactions (Table 1).

Experimental

P-Cresoloxyacetyl hydrazine (18.0 g, 0.10 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 until a clear solution was obtained. Carbon disulphide (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 ether (100 ml) 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 the above synthesized potassium dithiocarbazinate (29.4 g, 0.10 mol), hydrazine hydrate (99 %, 0.20 mol) and water (2 ml) was heated gently to boil for 30 minutes. Heating was continued until the evacuation of hydrogen sulphide ceased. 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 achieved from ethanol (Conti, 1964). The yield was 14.63 g, 62 %. M.p. 461-463 K.