3,5-Bis(4-hy­droxy­phen­yl)-4H-1,2,4-triazol-4-amine monohydrate

Sidik Silong; Mohamad Zaki Ab Rahman; Mansor Hj Ahmad; Huey Chong Kwong; Seik Weng Ng

doi:10.1107/S1600536810032915

. 2010 Aug 28;66(Pt 9):o2469. doi: 10.1107/S1600536810032915

3,5-Bis(4-hydroxyphenyl)-4H-1,2,4-triazol-4-amine monohydrate

Sidik Silong ^a, Mohamad Zaki Ab Rahman ^a, Mansor Hj Ahmad ^a, Huey Chong Kwong ^a, Seik Weng Ng ^b,^*

PMCID: PMC3008073 PMID: 21588787

Abstract

The triazole ring in the title compound, C₁₄H₁₂N₄O₂·H₂O, makes dihedral angles of 36.9 (1) and 37.3 (1)° with the two benzene rings. Each hydroxy group is a hydrogen-bond donor to a two-coordinate N atom of an adjacent molecule; these O—H⋯N hydrogen bonds generate a layer parallel to the ab plane. Adjacent layers are linked by N—-H⋯O and O_water—H⋯O hydrogen bonds into a three-dimensional network.

Related literature

For two modifications of 4-amino-3,5-diphenyl-1,2,4-triazole, see: Ikemi et al. (2002 ▶); Zhang et al. (2009 ▶). For comparison structures, see: Wang et al. (2006 ▶); Zachara et al. (2004 ▶); Bentiss et al. (1998 ▶).

Experimental

Crystal data

C₁₄H₁₂N₄O₂·H₂O
M _r = 286.29
Orthorhombic,
a = 10.6659 (5) Å
b = 15.9790 (8) Å
c = 7.4632 (4) Å
V = 1271.96 (11) Å³
Z = 4
Cu Kα radiation
μ = 0.90 mm⁻¹
T = 100 K
0.30 × 0.10 × 0.05 mm

Data collection

Oxford Diffraction Gemini E diffractometer
Absorption correction: multi-scan (CrysAlis PRO; Oxford Diffraction, 2010 ▶) T _min = 0.773, T _max = 0.956
2460 measured reflections
1275 independent reflections
1172 reflections with I > 2σ(I)
R _int = 0.019

Refinement

R[F ² > 2σ(F ²)] = 0.034
wR(F ²) = 0.097
S = 1.05
1275 reflections
215 parameters
8 restraints
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.23 e Å⁻³
Δρ_min = −0.24 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: X-SEED (Barbour, 2001 ▶); software used to prepare material for publication: publCIF (Westrip, 2010 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536810032915/bt5326sup1.cif

e-66-o2469-sup1.cif^{(17.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810032915/bt5326Isup2.hkl

e-66-o2469-Isup2.hkl^{(63KB, 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
O1—H1o⋯N3ⁱ	0.84 (3)	1.92 (3)	2.730 (2)	163 (3)
O2—H2o⋯N4ⁱⁱ	0.84 (3)	2.02 (3)	2.850 (2)	168 (4)
O1w—H11⋯O2ⁱⁱⁱ	0.85 (3)	2.19 (3)	3.020 (3)	166 (4)
N1—H1n⋯O1w	0.87 (3)	2.08 (3)	2.943 (4)	173 (4)
N1—H2n⋯O1^iv	0.86 (3)	2.36 (3)	3.202 (4)	164 (3)

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

Acknowledgments

We thank the Ministry of Science, Technology and Innovation (grant No. 04–01–04-SF0144), Universiti Pertanian Malaysia and the University of Malaya for supporting this study.

supplementary crystallographic information

Comment

The class of 3,5-bis(n-hydroxyphenyl)-4-amino-1,2,4-triazoles represents a class of efficient corrosion inhibitors that are synthesized from n-hydroxybenzonitrile, hydrazine and hydrazine sulfate. The pure product is obtained in a number of steps that involve acidification/basification followed by recrystallization, as exemplified by 3,5-bis(4-hydroxyphenyl)-4-amino-1,2,4-triazole (Bentiss et al., 1998). The compound can be synthesized, more conveniently, though a microwave route. The compound is, in fact, a monohydrate (Scheme I, Fig. 1).

Experimental

4-Hydroxybenzonitrile (3 mmol), hydrazine dihydrochloride (1 mmol) and anhydrous hydrazine (3 mmol) along with n-butanol (3 ml) were placed in a microwave synthesizer tube. The tube was irradiated in a CEM Discovery Synthesizer. The magnetron was set to 'normal' and the temperature to 403 K. The tube was irradiated for 8 minutes. Water (10 ml) was added to dissolve the contents. The solution was set aside for the growth of the faint-yellow crystals, which separated after 3 days.