5-Amino-1H-1,2,4-triazol-4-ium hydrogen oxalate

Essid, M.; Marouani, H.; Al-Deyab, S.S.; Rzaigui, M.

doi:10.1107/S1600536813019363

organic compounds

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ISSN: 2056-9890

Volume 69| Part 8| August 2013| Page o1279

doi:10.1107/S1600536813019363

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5-Amino-1H-1,2,4-triazol-4-ium hydrogen oxalate

Manel Essid,^a ^* Houda Marouani,^a Salem S. Al-Deyab ^b and Mohamed Rzaigui ^a

^aLaboratoire de Chimie des Matériaux, Faculté des Sciences de Bizerte, 7021 Zarzouna Bizerte, Tunisia, and ^bChemistry Department, Faculty of Science, King Saud University, PO Box 2455, Riyadh 11451, Saudi Arabia
^*Correspondence e-mail: essidmanel@voila.fr

(Received 9 July 2013; accepted 13 July 2013; online 20 July 2013)

In the title salt, C₂H₅N₄⁺·C₂HO₄⁻, the hydrogen oxalate anions form corrugated chains parallel to the c axis, linked by intermolecular O—H⋯O hydrogen bonds. The 5-amino-1H-1,2,4-triazol-4-ium cations are connected into centrosymmetric clusters via weak C—H⋯N hydrogen bonds forming nine-membered rings with an R₃³(9) motif. These clusters are interconnected via anions through N—H⋯O hydrogen bonds, building a three-dimensional network.

Related literature

For the properties of triazoles, see: Li et al. (2004 ); Mernari et al. (1998 ); Bentiss et al. (1999 ). For graph-set notation of hydrogen bonding, see: Bernstein et al. (1995 ). For related structures, see: Matulková et al. (2007 , 2008 ).

Experimental

Crystal data

C₂H₅N₄⁺·C₂HO₄⁻
M_r = 174.13
Trigonal, $[R \overline 3]$
a = 23.093 (4) Å
c = 6.603 (3) Å
V = 3049.3 (16) Å³
Z = 18
Ag Kα radiation
λ = 0.56080 Å
μ = 0.09 mm⁻¹
T = 293 K
0.35 × 0.3 × 0.25 mm

Data collection

Enraf–Nonius CAD-4 diffractometer
3909 measured reflections
3313 independent reflections
1929 reflections with I > 2σ(I)
R_int = 0.023
2 standard reflections every 120 min intensity decay: 1%

Refinement

R[F² > 2σ(F²)] = 0.060
wR(F²) = 0.194
S = 1.04
3313 reflections
121 parameters
H atoms treated by a mixture of independent and constrained refinement
Δρ_max = 0.50 e Å⁻³
Δρ_min = −0.42 e Å⁻³

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O1—H1⋯O3ⁱ	0.87 (3)	1.72 (3)	2.5845 (17)	174 (3)
N1—H2⋯O1ⁱⁱ	0.86 (3)	2.29 (3)	3.087 (2)	155 (2)
N1—H3⋯O4ⁱⁱⁱ	0.88 (3)	2.06 (3)	2.925 (2)	171 (3)
N2—H4⋯O4^iv	0.86	2.09	2.892 (2)	154
N2—H4⋯O2^iv	0.86	2.28	2.878 (2)	127
N3—H5⋯O3ⁱⁱⁱ	0.86	1.94	2.7652 (18)	161
C4—H6⋯N4^v	0.93	2.41	3.313 (3)	165
Symmetry codes: (i) $[-x+y+{\script{2\over 3}}, -x+{\script{1\over 3}}, z+{\script{1\over 3}}]$ ; (ii) $[-x+y+{\script{2\over 3}}, -x+{\script{1\over 3}}, z-{\script{2\over 3}}]$ ; (iii) -x+1, -y, -z; (iv) $[x-y-{\script{1\over 3}}, x-{\script{2\over 3}}, -z+{\script{1\over 3}}]$ ; (v) -y, x-y-1, z.

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994 ); cell refinement: CAD-4 EXPRESS; data reduction: XCAD4 (Harms & Wocadlo, 1995 ); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008 ); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012 ); software used to prepare material for publication: WinGX (Farrugia, 2012).

Supporting information

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536813019363/pv2640sup1.cif

Structure factors: contains datablock I. DOI: 10.1107/S1600536813019363/pv2640Isup2.hkl

Supporting information file. DOI: 10.1107/S1600536813019363/pv2640Isup3.cml

checkCIF report

Comment top

Triazole derivatives are used in the synthesis of antibiotics, fungicides, herbicides, plant growth hormone regulators (Li et al., 2004), and potentially good corrosion inhibitors (Mernari et al., 1998; Bentiss et al., 1999). Materials based on triazole compounds with dicarboxylic acids (4-amino-1,2,4-triazol-1-ium oxalate, adducts of 4-amino-1,2,4-triazole with succinic acid and adipic acid and 3-amino-1,2,4-triazolinium hydrogen L-tartrate) were also prepared and characterized as promising compounds in the field of non linear optics (Matulková et al., 2008; Matulková et al., 2007).

The asymmetric unit of the title salt (Fig. 1) contains a 5-amino-1,2,4-triazol-4-ium cation and an oxalate anion. The cation is monoprotonated at atom N2 and oxalic acid is mono-deprotonated. Geometrical parameters of the cation are found to be in agreement with those of other similar structures of 3-amino-1,2,4-triazolinium(1+) hydrogen L-tartrate (Matulková et al., 2007).

The crystal structure is based on a three dimensional network of hydrogen oxalic acid anions interconnected by O—H···O hydrogen bonds with lengths of 2.585 Å.

Planar 5-amino-1,2,4-triazolinium cations are located in the cavities of the hydrogen oxalic acid network and connected with anions via linear and bifurcated N—H···O hydrogen bonds. The donor-acceptor distances in these hydrogen bonds attain values from 2.765 to 3.087 Å (Tab. 1 and Fig. 2).

The oxalate ion is maintained by moderate hydrogen bonds that link the oxygen atoms of oxalate ion and the hydrogen of the other oxalate into corrugated chains parallel to the c axis. In addition, there are weak C—H···N hydrogen bonds in the crystal structure between 5-amino-1,2,4-triazilium cations forming an R₃³(9) motif (Fig. 2) (Bernstein et al., 1995). These cations are interconnected via anions through N—H···O hydrogen bonds, building a three dimensional network.

Related literature top

For the properties of triazoles, see: Li et al. (2004); Mernari et al. (1998); Bentiss et al. (1999). For graph-set notation of hydrogen bonding, see: Bernstein et al. (1995). For related structures, see: Matulková et al. (2007, 2008).

Experimental top

An aqueous solution of H₂C₂O₄ (2 mmol in 10 ml water) was added to an aqueous solution of 5-amino-1H-1,2,4-triazole (2 mmol in 10 ml of water). The obtained solution was stirred at 333 K for 30 min and then left to stand at room temperature. Colorless single crystals of the title compound were obtained after some days.

Computing details top

Data collection: CAD-4 EXPRESS (Enraf–Nonius, 1994); cell refinement: CAD-4 EXPRESS (Enraf–Nonius, 1994); data reduction: XCAD4 (Harms & Wocadlo, 1995); program(s) used to solve structure: SHELXS86 (Sheldrick, 2008); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: WinGX (Farrugia, 2012).

Figures top

	Fig. 1. An ORTEP view of the title salt with the atom-labelling scheme. Displacement ellipsoids are drawn at the 30% probability level. H atoms are represented as small spheres of arbitrary radii.
	Fig. 2. A view of the hydrogen bonds (dotted lines) in the crystal structure of the title salt. H atoms non-participating in hydrogen- bonding were omitted for clarity.

(I) top

Crystal data top

C₂H₅N₄⁺·C₂HO₄⁻	D_x = 1.707 Mg m⁻³
M_r = 174.13	Ag Kα radiation, λ = 0.56080 Å
Trigonal, R3	Cell parameters from 25 reflections
Hall symbol: -R 3	θ = 9–11°
a = 23.093 (4) Å	µ = 0.09 mm⁻¹
c = 6.603 (3) Å	T = 293 K
V = 3049.3 (16) Å³	Prism, colorless
Z = 18	0.35 × 0.3 × 0.25 mm
F(000) = 1620

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.023
Radiation source: fine-focus sealed tube	θ_max = 28.0°, θ_min = 2.4°
Graphite monochromator	h = −1→33
non–profiled ω scans	k = −1→33
3909 measured reflections	l = −11→11
3313 independent reflections	2 standard reflections every 120 min
1929 reflections with I > 2σ(I)	intensity decay: 1%

Refinement top

Refinement on F²	Primary atom site location: structure-invariant direct methods
Least-squares matrix: full	Secondary atom site location: difference Fourier map
R[F² > 2σ(F²)] = 0.060	Hydrogen site location: inferred from neighbouring sites
wR(F²) = 0.194	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	w = 1/[σ²(F_o²) + (0.0979P)² + 1.6007P] where P = (F_o² + 2F_c²)/3
3313 reflections	(Δ/σ)_max < 0.001
121 parameters	Δρ_max = 0.50 e Å⁻³
0 restraints	Δρ_min = −0.42 e Å⁻³

Crystal data top

C₂H₅N₄⁺·C₂HO₄⁻	Z = 18
M_r = 174.13	Ag Kα radiation, λ = 0.56080 Å
Trigonal, R3	µ = 0.09 mm⁻¹
a = 23.093 (4) Å	T = 293 K
c = 6.603 (3) Å	0.35 × 0.3 × 0.25 mm
V = 3049.3 (16) Å³

Data collection top

Enraf–Nonius CAD-4 diffractometer	R_int = 0.023
3909 measured reflections	2 standard reflections every 120 min
3313 independent reflections	intensity decay: 1%
1929 reflections with I > 2σ(I)

Refinement top

R[F² > 2σ(F²)] = 0.060	0 restraints
wR(F²) = 0.194	H atoms treated by a mixture of independent and constrained refinement
S = 1.04	Δρ_max = 0.50 e Å⁻³
3313 reflections	Δρ_min = −0.42 e Å⁻³
121 parameters

Special details top

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 (Å²) top

	x	y	z	U_iso*/U_eq
O1	0.35441 (6)	−0.03841 (6)	0.4263 (2)	0.0279 (3)
O4	0.50310 (6)	−0.02945 (6)	0.2759 (2)	0.0304 (3)
O3	0.46709 (6)	0.04345 (6)	0.2350 (2)	0.0268 (3)
O2	0.37748 (7)	−0.12148 (6)	0.4035 (3)	0.0384 (4)
N3	0.40979 (7)	−0.14645 (7)	−0.1112 (2)	0.0282 (3)
H5	0.4515	−0.1183	−0.1295	0.034*
N1	0.36951 (8)	−0.06980 (8)	−0.0972 (3)	0.0310 (3)
N2	0.30499 (7)	−0.18848 (8)	−0.0659 (3)	0.0308 (3)
H4	0.2661	−0.1927	−0.0501	0.037*
C3	0.36142 (7)	−0.13134 (8)	−0.0947 (2)	0.0228 (3)
C2	0.46067 (7)	−0.01195 (7)	0.2875 (2)	0.0205 (3)
C4	0.31868 (9)	−0.23999 (9)	−0.0656 (3)	0.0338 (4)
H6	0.2877	−0.2851	−0.0480	0.041*
C1	0.39246 (8)	−0.06374 (7)	0.3785 (2)	0.0217 (3)
N4	0.38176 (9)	−0.21484 (9)	−0.0939 (3)	0.0429 (4)
H1	0.3155 (15)	−0.0699 (15)	0.467 (4)	0.054 (8)*
H3	0.4074 (14)	−0.0368 (14)	−0.142 (4)	0.049 (7)*
H2	0.3342 (14)	−0.0667 (12)	−0.113 (4)	0.039 (6)*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
O1	0.0205 (5)	0.0209 (5)	0.0446 (7)	0.0121 (4)	0.0104 (5)	0.0068 (5)
O4	0.0229 (5)	0.0301 (6)	0.0442 (7)	0.0179 (5)	0.0058 (5)	0.0057 (5)
O3	0.0183 (5)	0.0208 (5)	0.0405 (7)	0.0091 (4)	0.0014 (5)	0.0076 (5)
O2	0.0334 (7)	0.0216 (6)	0.0648 (10)	0.0172 (5)	0.0158 (6)	0.0122 (6)
N3	0.0185 (6)	0.0235 (6)	0.0423 (8)	0.0103 (5)	0.0040 (5)	0.0025 (6)
N1	0.0276 (7)	0.0244 (7)	0.0437 (9)	0.0149 (6)	−0.0001 (6)	0.0016 (6)
N2	0.0159 (5)	0.0274 (7)	0.0448 (9)	0.0076 (5)	0.0030 (5)	0.0023 (6)
C3	0.0170 (6)	0.0235 (7)	0.0270 (7)	0.0093 (5)	0.0004 (5)	−0.0004 (5)
C2	0.0177 (6)	0.0206 (6)	0.0237 (7)	0.0101 (5)	0.0000 (5)	0.0008 (5)
C4	0.0219 (7)	0.0183 (7)	0.0541 (12)	0.0047 (6)	0.0015 (7)	0.0026 (7)
C1	0.0203 (6)	0.0195 (6)	0.0279 (7)	0.0120 (5)	0.0022 (5)	0.0037 (5)
N4	0.0336 (9)	0.0314 (8)	0.0665 (12)	0.0184 (7)	0.0035 (8)	0.0027 (8)

Geometric parameters (Å, º) top

O1—C1	1.3143 (19)	N1—H3	0.88 (3)
O1—H1	0.87 (3)	N1—H2	0.86 (3)
O4—C2	1.2351 (19)	N2—C3	1.325 (2)
O3—C2	1.2607 (18)	N2—C4	1.375 (2)
O2—C1	1.2099 (19)	N2—H4	0.8600
N3—C3	1.331 (2)	C2—C1	1.546 (2)
N3—N4	1.380 (2)	C4—N4	1.284 (3)
N3—H5	0.8600	C4—H6	0.9300
N1—C3	1.338 (2)

C1—O1—H1	110.1 (19)	N3—C3—N1	126.00 (15)
C3—N3—N4	108.56 (14)	O4—C2—O3	127.23 (15)
C3—N3—H5	125.7	O4—C2—C1	116.06 (13)
N4—N3—H5	125.7	O3—C2—C1	116.71 (13)
C3—N1—H3	118.4 (19)	N4—C4—N2	107.94 (15)
C3—N1—H2	117.1 (17)	N4—C4—H6	126.0
H3—N1—H2	118 (2)	N2—C4—H6	126.0
C3—N2—C4	108.94 (14)	O2—C1—O1	124.85 (15)
C3—N2—H4	125.5	O2—C1—C2	121.67 (14)
C4—N2—H4	125.5	O1—C1—C2	113.47 (12)
N2—C3—N3	106.69 (14)	C4—N4—N3	107.86 (15)
N2—C3—N1	127.24 (15)

C4—N2—C3—N3	−0.3 (2)	O3—C2—C1—O2	168.06 (17)
C4—N2—C3—N1	−177.35 (19)	O4—C2—C1—O1	166.66 (15)
N4—N3—C3—N2	0.6 (2)	O3—C2—C1—O1	−12.8 (2)
N4—N3—C3—N1	177.71 (18)	N2—C4—N4—N3	0.5 (2)
C3—N2—C4—N4	−0.1 (2)	C3—N3—N4—C4	−0.7 (2)
O4—C2—C1—O2	−12.5 (2)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.87 (3)	1.72 (3)	2.5845 (17)	174 (3)
N1—H2···O1ⁱⁱ	0.86 (3)	2.29 (3)	3.087 (2)	155 (2)
N1—H3···O4ⁱⁱⁱ	0.88 (3)	2.06 (3)	2.925 (2)	171 (3)
N2—H4···O4^iv	0.86	2.09	2.892 (2)	154
N2—H4···O2^iv	0.86	2.28	2.878 (2)	127
N3—H5···O3ⁱⁱⁱ	0.86	1.94	2.7652 (18)	161
C4—H6···N4^v	0.93	2.41	3.313 (3)	165

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

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
O1—H1···O3ⁱ	0.87 (3)	1.72 (3)	2.5845 (17)	174 (3)
N1—H2···O1ⁱⁱ	0.86 (3)	2.29 (3)	3.087 (2)	155 (2)
N1—H3···O4ⁱⁱⁱ	0.88 (3)	2.06 (3)	2.925 (2)	171 (3)
N2—H4···O4^iv	0.86	2.09	2.892 (2)	154.4
N2—H4···O2^iv	0.86	2.28	2.878 (2)	126.7
N3—H5···O3ⁱⁱⁱ	0.86	1.94	2.7652 (18)	161.0
C4—H6···N4^v	0.93	2.41	3.313 (3)	164.9

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

Acknowledgements

This work was supported by the Tunisian Ministry of HEScR. The authors are grateful to the Deanship of Scientific Research at King Saud University for funding the paper through the Research Group Project No. RGP-VPP-089.

References

Bentiss, F., Langrenée, M., Traisnel, M. & Hornez, J. C. (1999). Corros. Sci. 41, 789–803. Web of Science CrossRef CAS Google Scholar
Bernstein, J., David, R. E., Shimoni, L. & Chang, N.-L. (1995). Angew. Chem. Int. Ed. Engl. 34, 1555–1573. CrossRef CAS Web of Science Google Scholar
Enraf–Nonius (1994). CAD-4 EXPRESS. Enraf–Nonius, Delft, The Netherlands. Google Scholar
Farrugia, L. J. (2012). J. Appl. Cryst. 45, 849–854. Web of Science CrossRef CAS IUCr Journals Google Scholar
Harms, K. & Wocadlo, S. (1995). XCAD4. University of Marburg, Germany. Google Scholar
Li, W., Wu, Q., Yu, Y., Luo, M., Hu, L., Gu, Y., Niu, F. & Hu, J. (2004). Spectrochim. Acta Part A, 60, 2343–2354. CrossRef Google Scholar
Matulková, I., Císařová, I., Němec, P. & Mička, Z. (2007). J. Mol. Struct. 834–836, 328–335. Google Scholar
Matulková, I., Němec, I., Teubner, K., Němec, P. & Mička, Z. (2008). J. Mol. Struct. 873, 46–60. Google Scholar
Mernari, B., Elattari, H., Traisnel, M., Bentiss, F. & Langrenée, M. (1998). Corros. Sci. 40, 391–399. Web of Science CrossRef CAS Google Scholar
Sheldrick, G. M. (2008). Acta Cryst. A64, 112–122. Web of Science CrossRef CAS IUCr Journals Google Scholar