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

The crystal structure of the title compound, 2C₃H₅N₄O₂⁺·SO₄²⁻·2H₂O, displays a three-dimensional framework in which mixed infinite chains [oriented parallel to (510) and (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 R₄⁴(14) and R₄²(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⁺·SO₄²⁻·2H₂O

• M_r = 390.31

• Monoclinic, C 2/c

• a = 19.4350 (9) Å

• b = 5.8467 (2) Å

• c = 13.3343 (6) Å

• β = 109.981 (2)°

• V = 1423.98 (10) ų

• 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[F² > 2σ(F²)] = 0.029

• wR(F²) = 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

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⋯O1^i	0.89 (2)	1.93 (2)	2.7941 (17)	163 (2)
O2—H2⋯O1W^ii	0.82	1.74	2.5403 (16)	165
N1—H1⋯O4^iii	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
Symmetry codes: (i) ; (ii) ; (iii) -x+1, -y+1, -z+1; (iv) ; (v) -x+1, -y, -z+1; (vi) x, y-1, z.

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).

Supporting information

S1. 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).

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).

S2. 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.

S3. Refinement

The H atoms of the water molecules were located in difference Fourier maps and were refined with U_iso(H) = 1.5U_eq(O). The remaining H atoms were located in difference Fourier maps but introduced in calculated positions and treated as riding on their parent atoms (N or O) with, O—H = 0.82 Å and N—H = 0.86 Å with U_iso(H) = 1.2 U_eq(N) and U_iso(H) = 1.5 U_eq(O).

Computing details

Data collection: APEX2 (Bruker,2001); cell refinement: SAINT (Bruker, 2001); data reduction: SAINT (Bruker, 2001); 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).

Figures

	Fig. 1. The molecular structure of the title compound with the atomic labeling scheme. Displacement are drawn at the 50% probability level. Hydrogen bonds are shown as dashed lines.
	Fig. 2. (Brandenburg & Berndt, 2001) A diagram of the three-dimensional packing of (I). (510) and (-510) planes have been presented to illustrate the mixed infinite chains. Hydrogen bonds are shown as dashed lines.
	Fig. 3. (Brandenburg & Berndt, 2001) A view of the mixed infinite chain. Hydrogen bonds are shown as dashed lines.

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

Crystal data

2C3H5N4O2^+·SO4^2^−·2H2O	F(000) = 808
Mr = 390.31	Dx = 1.821 Mg m^−3
Monoclinic, C2/c	Mo Kα radiation, λ = 0.71073 Å
a = 19.4350 (9) Å	Cell parameters from 1620 reflections
b = 5.8467 (2) Å	θ = 3.3–27.4°
c = 13.3343 (6) Å	µ = 0.31 mm^−1
β = 109.981 (2)°	T = 150 K
V = 1423.98 (10) Å^3	Needle, colourless
Z = 4	0.48 × 0.08 × 0.06 mm

Data collection

Bruker APEXII diffractometer	Rint = 0.032
Graphite monochromator	θmax = 27.5°, θmin = 3.3°
CCD rotation images, thin slices scans	h = −24→25
11018 measured reflections	k = −7→7
1620 independent reflections	l = −17→15
1470 reflections with I > 2σ(I)

Refinement

Refinement on F^2	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F^2 > 2σ(F^2)] = 0.029	Hydrogen site location: inferred from neighbouring sites
wR(F^2) = 0.077	H atoms treated by a mixture of independent and constrained refinement
S = 1.08	w = 1/[σ^2(Fo^2) + (0.0343P)^2 + 1.9446P] where P = (Fo^2 + 2Fc^2)/3
1620 reflections	(Δ/σ)max = 0.009
121 parameters	Δρmax = 0.37 e Å^−3
0 restraints	Δρmin = −0.41 e Å^−3

Special details

Geometry. All e.s.d.'s (except the e.s.d. in the dihedral angle between two l.s. planes) are estimated using the full covariance matrix. The cell e.s.d.'s are taken into account individually in the estimation of e.s.d.'s in distances, angles and torsion angles; correlations between e.s.d.'s in cell parameters are only used when they are defined by crystal symmetry. An approximate (isotropic) treatment of cell e.s.d.'s is used for estimating e.s.d.'s involving l.s. planes.

Refinement. Refinement of F² against ALL reflections. The weighted R-factor wR and goodness of fit S are based on F², conventional R-factors R are based on F, with F set to zero for negative F². The threshold expression of F² > σ(F²) is used only for calculating R-factors(gt) etc. and is not relevant to the choice of reflections for refinement. R-factors based on F² are statistically about twice as large as those based on F, and R- factors based on ALL data will be even larger.

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Ų)

	x	y	z	Uiso*/Ueq
C1	0.32927 (7)	0.3566 (2)	0.60560 (11)	0.0136 (3)
C2	0.35578 (7)	0.2304 (2)	0.52873 (11)	0.0123 (3)
C3	0.40656 (7)	−0.0381 (2)	0.46589 (11)	0.0129 (3)
N1	0.38002 (6)	0.1265 (2)	0.39270 (9)	0.0138 (3)
H1	0.3827	0.125	0.3296	0.017*
N2	0.34797 (6)	0.2981 (2)	0.43222 (9)	0.0138 (3)
N3	0.39065 (6)	0.0245 (2)	0.55278 (9)	0.0123 (2)
H3	0.4005	−0.0502	0.6116	0.015*
N4	0.44239 (7)	−0.2252 (2)	0.45703 (10)	0.0169 (3)
H4A	0.451	−0.2519	0.399	0.02*
H4B	0.4571	−0.3201	0.5093	0.02*
O1	0.33947 (6)	0.28073 (19)	0.69430 (8)	0.0188 (2)
O2	0.29439 (6)	0.54386 (18)	0.56322 (8)	0.0186 (2)
H2	0.2817	0.612	0.6077	0.028*
O3	0.48758 (5)	0.50548 (17)	0.65377 (8)	0.0158 (2)
O4	0.56503 (6)	0.79464 (19)	0.76558 (8)	0.0190 (2)
S1	0.5	0.64445 (8)	0.75	0.01101 (13)
O1W	0.25419 (6)	0.69140 (19)	0.32536 (9)	0.0194 (2)
H1W	0.2751 (11)	0.724 (4)	0.2772 (17)	0.029*
H2W	0.2786 (11)	0.586 (4)	0.3624 (17)	0.029*

Atomic displacement parameters (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
C1	0.0118 (6)	0.0150 (7)	0.0148 (7)	−0.0021 (5)	0.0054 (5)	−0.0017 (5)
C2	0.0117 (6)	0.0128 (6)	0.0122 (7)	−0.0015 (5)	0.0037 (5)	−0.0008 (5)
C3	0.0119 (6)	0.0151 (7)	0.0117 (6)	−0.0026 (5)	0.0040 (5)	−0.0008 (5)
N1	0.0177 (6)	0.0155 (6)	0.0097 (6)	0.0011 (5)	0.0066 (5)	−0.0003 (4)
N2	0.0150 (6)	0.0143 (6)	0.0126 (6)	−0.0001 (4)	0.0053 (5)	−0.0008 (4)
N3	0.0145 (5)	0.0138 (6)	0.0093 (5)	0.0010 (4)	0.0052 (4)	0.0015 (4)
N4	0.0220 (6)	0.0162 (6)	0.0145 (6)	0.0034 (5)	0.0087 (5)	−0.0002 (5)
O1	0.0230 (5)	0.0213 (5)	0.0155 (5)	0.0024 (4)	0.0108 (4)	0.0015 (4)
O2	0.0227 (5)	0.0175 (5)	0.0170 (5)	0.0062 (4)	0.0086 (4)	−0.0006 (4)
O3	0.0182 (5)	0.0164 (5)	0.0125 (5)	−0.0004 (4)	0.0051 (4)	−0.0035 (4)
O4	0.0221 (5)	0.0243 (6)	0.0133 (5)	−0.0105 (4)	0.0094 (4)	−0.0049 (4)
S1	0.0129 (2)	0.0119 (2)	0.0090 (2)	0	0.00474 (17)	0
O1W	0.0228 (6)	0.0202 (5)	0.0187 (6)	0.0065 (4)	0.0117 (5)	0.0044 (4)

Geometric parameters (Å, º)

C1—O1	1.2144 (18)	N3—H3	0.86
C1—O2	1.3098 (17)	N4—H4A	0.86
C1—C2	1.4905 (19)	N4—H4B	0.86
C2—N2	1.3046 (18)	O2—H2	0.82
C2—N3	1.3648 (18)	O3—S1	1.4674 (10)
C3—N4	1.3236 (19)	O4—S1	1.4941 (10)
C3—N1	1.3420 (18)	S1—O3^i	1.4674 (10)
C3—N3	1.3480 (18)	S1—O4^i	1.4941 (10)
N1—N2	1.3774 (17)	O1W—H1W	0.89 (2)
N1—H1	0.86	O1W—H2W	0.83 (2)
O1—C1—O2	127.86 (13)	C3—N3—H3	126.9
O1—C1—C2	120.61 (13)	C2—N3—H3	126.9
O2—C1—C2	111.50 (12)	C3—N4—H4A	120
N2—C2—N3	112.37 (12)	C3—N4—H4B	120
N2—C2—C1	125.24 (13)	H4A—N4—H4B	120
N3—C2—C1	122.38 (12)	C1—O2—H2	109.5
N4—C3—N1	127.67 (13)	O3—S1—O3^i	112.76 (9)
N4—C3—N3	125.69 (13)	O3—S1—O4	109.00 (6)
N1—C3—N3	106.63 (12)	O3^i—S1—O4	108.98 (6)
C3—N1—N2	110.85 (11)	O3—S1—O4^i	108.98 (6)
C3—N1—H1	124.6	O3^i—S1—O4^i	109.00 (6)
N2—N1—H1	124.6	O4—S1—O4^i	108.01 (9)
C2—N2—N1	103.94 (11)	H1W—O1W—H2W	106.3 (19)
C3—N3—C2	106.20 (11)
O1—C1—C2—N2	−179.54 (13)	C1—C2—N2—N1	−179.34 (12)
O2—C1—C2—N2	2.06 (19)	C3—N1—N2—C2	−0.42 (14)
O1—C1—C2—N3	1.6 (2)	N4—C3—N3—C2	177.99 (13)
O2—C1—C2—N3	−176.82 (12)	N1—C3—N3—C2	−1.19 (14)
N4—C3—N1—N2	−178.13 (13)	N2—C2—N3—C3	1.00 (16)
N3—C3—N1—N2	1.03 (15)	C1—C2—N3—C3	−179.99 (12)
N3—C2—N2—N1	−0.37 (15)

Symmetry code: (i) −x+1, y, −z+3/2.

Hydrogen-bond geometry (Å, º)

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···O1^ii	0.89 (2)	1.93 (2)	2.7941 (17)	163 (2)
O2—H2···O1W^iii	0.82	1.74	2.5403 (16)	165
N1—H1···O4^iv	0.86	1.94	2.7107 (16)	149
N3—H3···O4^v	0.86	1.79	2.6436 (15)	171
N4—H4A···O3^vi	0.86	2.17	2.8452 (17)	136
N4—H4B···O3^vii	0.86	2.08	2.9255 (16)	168

Symmetry codes: (ii) x, −y+1, z−1/2; (iii) −x+1/2, −y+3/2, −z+1; (iv) −x+1, −y+1, −z+1; (v) −x+1, y−1, −z+3/2; (vi) −x+1, −y, −z+1; (vii) x, y−1, z.

 

Footnotes

‡Current address: Département Sciences de la Matière, Faculté des Sciences Exactes et Sciences de la Nature et de la Vie, Université Larbi Ben M'hidi, 04000 Oum El Bouaghi, Algeria.