4-Amino-3-[(4-methoxy­phen­yl)amino­meth­yl]-1H-1,2,4-triazole-5(4H)-thione

Hoong-Kun Fun; Chin Sing Yeap; Shridhar Malladi; Mahesh Padaki; Arun M Isloor

doi:10.1107/S1600536809032607

. 2009 Aug 22;65(Pt 9):o2213. doi: 10.1107/S1600536809032607

4-Amino-3-[(4-methoxyphenyl)aminomethyl]-1H-1,2,4-triazole-5(4H)-thione

Hoong-Kun Fun ^a,^*,^‡, Chin Sing Yeap ^a,^§, Shridhar Malladi ^b, Mahesh Padaki ^b, Arun M Isloor ^b

PMCID: PMC2969966 PMID: 21577614

Abstract

The molecule of the title compound, C₁₀H₁₃N₅OS, is approximately planar, the dihedral angle between the triazole and benzene rings being 4.53 (10)°. The amino group adopts a pyramidal configuration. In the crystal structure, molecules are linked into two-dimensional networks parallel to (001) by intermolecular N—H⋯S and N—H⋯N hydrogen bonds. In addition, an S⋯S short contact of 3.3435 (7) Å is observed.

Related literature

For the pharmacological applications of 1,2,4-triazole derivatives, see: Amir et al. (2008 ▶); Isloor et al. (2009 ▶); Krzysztof et al. (2008 ▶); Kuş et al. (2008 ▶); Padmavathi et al. (2008 ▶). For the preparation, see: Holla & Udupa (1992 ▶). For related structures, see: Fun et al. (2009a ▶,b ▶). For the stability of the temperature controller used for data collection, see: Cosier & Glazer (1986 ▶).

Experimental

Crystal data

C₁₀H₁₃N₅OS
M _r = 251.31
Monoclinic,
a = 11.5142 (2) Å
b = 5.8804 (1) Å
c = 16.6891 (3) Å
β = 95.292 (1)°
V = 1125.17 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.28 mm⁻¹
T = 100 K
0.33 × 0.18 × 0.02 mm

Data collection

Bruker SMART APEXII CCD area-detector diffractometer
Absorption correction: multi-scan (SADABS; Bruker, 2005 ▶) T _min = 0.913, T _max = 0.994
5827 measured reflections
2365 independent reflections
2126 reflections with I > 2σ(I)
R _int = 0.024

Refinement

R[F ² > 2σ(F ²)] = 0.031
wR(F ²) = 0.068
S = 1.04
2365 reflections
171 parameters
1 restraint
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.33 e Å⁻³
Δρ_min = −0.26 e Å⁻³
Absolute structure: Flack (1983 ▶), 588 Friedel pairs
Flack parameter: 0.03 (7)

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/S1600536809032607/ci2889sup1.cif

e-65-o2213-sup1.cif^{(17.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809032607/ci2889Isup2.hkl

e-65-o2213-Isup2.hkl^{(116.2KB, 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	0.84 (2)	2.55 (2)	3.3672 (18)	164 (2)
N4—H1N4⋯N5ⁱⁱ	0.82 (3)	2.60 (3)	3.410 (2)	169 (3)
N5—H1N5⋯N1ⁱⁱⁱ	0.89 (2)	2.48 (2)	3.133 (2)	130 (2)

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

Acknowledgments

HKF thanks Universiti Sains Malaysia (USM) for the Research University Golden Goose grant No. 1001/PFIZIK/811012. CSY thanks USM for the award of a USM fellowship. AMI is grateful to the Head of the Department of Chemistry and Director, NITK, Surathkal, India, for providing research facilities.

supplementary crystallographic information

Comment

1,2,4-triazole and its derivatives were reported to exhibit various pharmacological activities such as antimicrobial, analgesic, anti-inflammatory, anticancer and antioxidant properties (Amir et al., 2008; Krzysztof et al., 2008; Kuş et al., 2008; Padmavathi et al., 2008). A few derivatives of triazoles have exhibited antimicrobial activity (Isloor et al., 2009). 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 the 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 the biological importance, we have synthesized the title compound and its crystal structure is reported here.

Bond lengths and angles in the title compound (Fig. 1) are comparable to those observed in related structures (Fun et al., 2009a,b). The molecule is approximately planar, with the dihedral angle between the triazole (N1/N2/C1/N3/C2) and benzene rings (C4-C9) being 4.53 (10)°.

In the crystal structure, the molecules are linked by intermolecular N2—H1N2···S1, N4—H1N4···N5 and N5—H1N5···N1 hydrogen bonds into a two-dimensional network parallel to ab plane (Fig. 2 and Table 1). In addition, a S···S(1-x, y, -z) short contact of 3.3435 (7) Å is observed.

Experimental

2-[(4-Methoxyphenyl)amino]acetohydrazide (19.5 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 dropwise and the contents were stirred vigorously. Further stirring was continued for 24 h. The resulting mixture (Holla & Udupa, 1992) was diluted with 100 ml of ether and the precipitate formed was collected by filtration, washed with dry ether and dried at 338 K under vacuum. It was used for the next step without any purification.

A mixture of above synthesized potassium dithiocarbazinate (30.9 g, 0.1 mol), hydrazine hydrate (99%, 0.2 mol) and water (2 ml) was gently heated to boil for 30 min. Heating was continued until the evaluation of hydrogen sulfide ceases. The reaction mixture was cooled to room temperature, diluted with water (100 ml) and acidified with 2 N HCl. The solid mass that separated was collected by filtration, washed with water and dried. Recrystallization was done from ethanol (yield: 15.1 g, 67.7%; m.p. 484–486 K).