Bis(5-amino-3-carb­oxy-1H-1,2,4-triazol-4-ium) sulfate dihydrate

Amira Ouakkaf; Fadila Berrah; Sofiane Bouacida; Thierry Roisnel

doi:10.1107/S1600536811013882

. 2011 Apr 16;67(Pt 5):o1171–o1172. doi: 10.1107/S1600536811013882

Bis(5-amino-3-carboxy-1H-1,2,4-triazol-4-ium) sulfate dihydrate

Amira Ouakkaf ^a, Fadila Berrah ^a,^*,^‡, Sofiane Bouacida ^b,^‡, Thierry Roisnel ^c

PMCID: PMC3089095 PMID: 21754477

Abstract

The crystal structure of the title compound, 2C₃H₅N₄O₂ ⁺·SO₄ ²⁻·2H₂O, displays a three-dimensional framework in which mixed infinite chains [oriented parallel to (510) and ( Inline graphic 10)] interfere, forming tunnels extending parallel to the c axis. Intermolecular O—H⋯O, N—H⋯O and O—H⋯N hydrogen bonds ensure the unity of the structure and generate centrosymmetric R ₄ ⁴(14) and R ₄ ²(8) rings. The S atom lies on a twofold axis.

Related literature

For uses of 1,2,4 triazole derivatives, see: Beckmann & Brooker, (2003 ▶); Bhargava et al. (1981 ▶); Fujigaya et al. (2003 ▶); Hirota et al. (1991 ▶); Li et al. (2004 ▶); Matulková et al. (2008 ▶). For related hybrid compounds, see: Berrah et al. (2011a ▶,b ▶,c ▶). For hydrogen-bond motifs, see: Bernstein et al. (1995 ▶); Etter et al. (1990 ▶).

Experimental

Crystal data

2C₃H₅N₄O₂ ⁺·SO₄ ²⁻·2H₂O
M _r = 390.31
Monoclinic,
a = 19.4350 (9) Å
b = 5.8467 (2) Å
c = 13.3343 (6) Å
β = 109.981 (2)°
V = 1423.98 (10) Å³
Z = 4
Mo Kα radiation
μ = 0.31 mm⁻¹
T = 150 K
0.48 × 0.08 × 0.06 mm

Data collection

Bruker APEXII diffractometer
11018 measured reflections
1620 independent reflections
1470 reflections with I > 2σ(I)
R _int = 0.032

Refinement

R[F ² > 2σ(F ²)] = 0.029
wR(F ²) = 0.077
S = 1.08
1620 reflections
121 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.37 e Å⁻³
Δρ_min = −0.41 e Å⁻³

Data collection: APEX2 (Bruker, 2001 ▶); cell refinement: SAINT (Bruker, 2001 ▶); data reduction: SAINT; program(s) used to solve structure: SIR2002 (Burla et al., 2005 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 for Windows (Farrugia, 1997 ▶) and DIAMOND (Brandenburg & Berndt, 2001 ▶); software used to prepare material for publication: WinGX (Farrugia, 1999 ▶).

Supplementary Material

Crystal structure: contains datablocks global, I. DOI: 10.1107/S1600536811013882/bq2295sup1.cif

e-67-o1171-sup1.cif^{(14.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536811013882/bq2295Isup2.hkl

e-67-o1171-Isup2.hkl^{(78.3KB, 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
O1W—H2W⋯N2	0.83 (2)	2.16 (2)	2.9774 (16)	169 (2)
O1W—H1W⋯O1ⁱ	0.89 (2)	1.93 (2)	2.7941 (17)	163 (2)
O2—H2⋯O1Wⁱⁱ	0.82	1.74	2.5403 (16)	165
N1—H1⋯O4ⁱⁱⁱ	0.86	1.94	2.7107 (16)	149
N3—H3⋯O4^iv	0.86	1.79	2.6436 (15)	171
N4—H4A⋯O3^v	0.86	2.17	2.8452 (17)	136
N4—H4B⋯O3^vi	0.86	2.08	2.9255 (16)	168

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

Acknowledgments

We are grateful to the LCATM Laboratory, Université Larbi Ben M′Hidi, Oum El Bouaghi, Algeria, for financial support.

supplementary crystallographic information

Comment

1,2,4-triazole derivatives are remarkable substances exhibiting a wide range of properties; while several compounds incorporating 1,2,4-triazole moieties show pharmacological and biological activities (antidepressants, anti-inflammatory, fungicides) (Bhargava et al., 1981; Hirota et al., 1991; Li et al., 2004), a number of them find use in material field and coordination chemistry (magnetic and non-linear optics properties, multidentate ligands) (Beckmann & Brooker, 2003; Fujigaya et al., 2003; Matulková et al., 2008).

Our recent investigation on some N-heterocycle compounds with inorganic acids (Berrah et al., 2011a,b,c), has revealed their ability to generate original networks stabilized in particular by hydrogen bonds; we report herein the structure of a new hybrid compound obtained from a disubstituted 1,2,4-triazole derivative (5-amino-1,2,4 triazol-1H-3-carboxylic acid hydrate) and the sulfuric acid.

The molecular structure and the atom-numbering scheme of the title compound are shown in Fig. 1. The sulfur atom lies in the twofold axis and the sulfate anion shows a quite regular geometry compared with that seen in similar compounds (Berrah et al., 2011b,c). The triazole ring exhibits a short distance of 1.3046 (18) Å revealing the double-bond character of the C2═N2 bond, two long distances 1.3648 (18) Å and 1.3774 (17) Å related to the single bonds C2—N3 and N1—N2, respectively. The C3—N1 and C3═ N3 bonds lengths are respectively 1.3420 (18) Å and 1.3480 (18) Å which suggests the delocalization of the double bond (N1 ≐C3 ≐N3).

The crystal structure of the title compound (Fig. 2) displays a three-dimensional framework where mixed infinite chains interfere to form tunnels parallel the c axis. According to their orientation, we can distinguish two kinds of chains: the first one directed along the (510) plane and the second along the (510) plane (Fig. 2). In a mixed chain, the cations adopt a head to head configuration in a way that NH₂, of two adjacent cations, are linked (via N—H···O hydrogen bonds) to two sulfate anions and C—OH are linked (by O—H···O hydrogen bonds) to two water molecules (Fig. 3) (Table 1). Consequently, centro-symmetric R⁴₄(14) and R²₄(8) graph-set rings are created (Etter et al., 1990; Bernstein et al., 1995).

Experimental

The title compound was synthesized by reacting 5-amino-1,2,4 triazol-1H-3-carboxylic acid hydrate with some excess of sulfuric acid in aqueous solution. Slow evaporation leads to well crystallized colorless needles.