4-Amino-3,5-dimethyl-4H1-,2,4-triazole–water (2/3)

Lin Cheng; Ya-Wen Zhang; Yan-Yan Sun; Gang Xu

doi:10.1107/S1600536808028146

. 2008 Sep 6;64(Pt 10):o1893. doi: 10.1107/S1600536808028146

4-Amino-3,5-dimethyl-4H1-,2,4-triazole–water (2/3)

Lin Cheng ^a,^*, Ya-Wen Zhang ^a, Yan-Yan Sun ^a, Gang Xu ^a

PMCID: PMC2959474 PMID: 21201105

Abstract

The asymmetric unit of the title compound, 2C₄H₈N₄·3H₂O, contains two crystallographically independent 4-amino-3,5-dimethyl-1,2,4-triazole molecules and three water molecules. The structure exhibits N—H⋯O, O—H⋯N and O—H⋯O hydrogen bonds.

Related literature

For related structures, see: Wang et al. (2006 ▶); Zachara et al. 2004 ▶). For related literature, see: Beckmann & Brooker (2003 ▶); Bentiss et al. (1999 ▶); Collin et al. (2003 ▶); Curtis (2004 ▶).

Experimental

Crystal data

2C₄H₈N₄·3H₂O
M _r = 278.34
Triclinic,
a = 7.194 (4) Å
b = 8.680 (4) Å
c = 13.592 (7) Å
α = 72.332 (8)°
β = 84.993 (8)°
γ = 68.936 (7)°
V = 754.5 (6) Å³
Z = 2
Mo Kα radiation
μ = 0.10 mm⁻¹
T = 293 (2) K
0.20 × 0.18 × 0.17 mm

Data collection

Bruker APEX CCD diffractometer
Absorption correction: multi-scan (SADABS; Sheldrick, 2000 ▶) T _min = 0.981, T _max = 0.984
5166 measured reflections
2904 independent reflections
2447 reflections with I > 2σ(I)
R _int = 0.014

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.137
S = 1.03
2904 reflections
213 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.27 e Å⁻³
Δρ_min = −0.22 e Å⁻³

Data collection: SMART (Bruker, 2000 ▶); cell refinement: SAINT (Bruker, 2000 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808028146/bt2782sup1.cif

e-64-o1893-sup1.cif^{(17KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808028146/bt2782Isup2.hkl

e-64-o1893-Isup2.hkl^{(142.5KB, 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
N4—H4D⋯O1W	0.93 (2)	2.00 (2)	2.924 (3)	170.9 (18)
N4—H4E⋯O3Wⁱ	0.88 (2)	2.21 (2)	3.078 (3)	168.3 (18)
N8—H8E⋯O2Wⁱⁱ	0.93 (3)	2.23 (3)	3.104 (3)	156 (2)
O1W—H1WA⋯O2Wⁱⁱⁱ	0.84 (3)	1.95 (3)	2.793 (3)	173 (3)
O1W—H1WB⋯O3W^iv	0.92 (3)	1.93 (3)	2.810 (2)	160 (3)
O2W—H2WA⋯N2	0.87 (3)	2.02 (3)	2.885 (2)	171 (2)
O2W—H2WB⋯N5	0.90 (3)	1.93 (3)	2.816 (2)	168 (2)
O3W—H3WA⋯N1	0.88 (2)	1.92 (2)	2.787 (2)	168 (2)
O3W—H3WB⋯N6	0.89 (3)	1.93 (3)	2.827 (2)	176 (2)

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

Acknowledgments

The authors thank the Program for Young Excellent Talents in Southeast University for financial support.

supplementary crystallographic information

Comment

The derivatives of 4-amino-1,2,4-triazoles have considerable importance in medicinal chemistry, agricultural and industrial chemistry (Bentiss et al. 1999; Collin et al. 2003; Curtis et al. 2004). They have also been used as multidentate ligands in coordination chemistry (Beckmann et al. 2003). Here, we report a hydrated 4-amino-1,2,4-triazole (mta)₂.3H₂O (mta = 4-amino-3,5-dimethyl-1,2,4-triazole).

The asymmetric unit of the title compound contains two crystallographically independent mta molecules and three water molecules. The C═N—N—C fragments of the tetrazine rings have the C═N distances of 1.299 (2), 1.300 (2) and 1.304 (2) Å, and the N—N distances of 1.392 (2) and 1.389 (2) Å. All other C—N distances are between 1.352 (2) and 1.362 (2) Å, which are considered to have part double-bond character. In the crystalline state, the mta and crystal water molecules are linked together by N—H···O, O—H···N and O—H···O hydrogen bonding.

Experimental

To a solution of mta (mta = 4-amino-3,5-dimethyl-1,2,4-triazole) (0.0228 g, 0.2 mmol) in CH₃OH (5 ml), an aqueous solution (5 ml) of MnSO₄.H₂O (0.0169 g, 0.1 mmol) was added. The mixture was stirred for half an hour and filtered. The filtrate was allowed to evaporate slowly at room temperature. After several days, colorless block crystals were obtained in 5% yield (0.0007 g) based on mta.