3,5-Di­amino-4H-1,2,4-triazol-1-ium 4-nitro­benzoate dihydrate

Lahmidi, S.; Essassi, E.M.; Benchidmi, M.; Saadi, M.; El Ammari, L.

doi:10.1107/S2414314617001596

organic compounds

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ISSN: 2414-3146

Volume 2| Part 2| February 2017| x170159

https://doi.org/10.1107/S2414314617001596

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3,5-Diamino-4H-1,2,4-triazol-1-ium 4-nitrobenzoate dihydrate

Sanae Lahmidi,^a El Mokhtar Essassi,^a ^* Mohammed Benchidmi,^a Mohamed Saadi ^b and Lahcen El Ammari ^b

^aLaboratoire de Chimie Organique Hétérocyclique URAC 21, Pôle de Compétences Pharmacochimie, Mohammed V University in Rabat, BP 1014 Avenue Ibn Batouta, Rabat , Morocco, and ^bLaboratoire de Chimie du Solide Appliquée, Faculty of Sciences, Mohammed V University in Rabat, Avenue Ibn Battouta, BP 1014, Rabat, Morocco
^*Correspondence e-mail: em_essassi@yahoo.fr

Edited by E. R. T. Tiekink, Sunway University, Malaysia (Received 29 January 2017; accepted 30 January 2017; online 3 February 2017)

The crystal of the title salt hydrate, C₂H₆N₅⁺·C₇H₄NO₄⁻·2H₂O, is built up from a 3,5-diamino-4H-1,2,4-triazol-1-ium cation linked to a 4-nitrobenzoate anion and to two water molecules through strong hydrogen bonds. The triazolyl ring is virtually planar, with the maximum deviation from the mean plane being 0.003 (1) Å. Small twists are noted in the anion with the dihedral angles between the ring and carboxylate and nitro groups being 7.82 (13) and 9.10 (15)°, respectively. In the crystal, molecules are linked by N—H⋯O, N—H⋯N, O—H⋯O and C—H⋯O interactions, forming layers parallel to (-101). The sheets are linked by O—H⋯O hydrogen bonds and π–π interactions between triazole and benzene rings [inter-centroid separation = 3.4967 (8) Å] to form a three-dimensional structure.

Keywords: crystal structure; salt; hydrate; benzoate; triazole; hydrogen bonding.

CCDC reference: 1530351

Structure description

Guanazole (3,5-diamino-1,2,4-triazole) derivatives, attract an interest and are actively studied as ligands in the synthesis of d-metal complexes (Aznar et al., 2006 ), precursors of condensed N-heterocyclic systems (Fernandes et al., 2015 ), corrosion inhibitors (El Issami et al., 2007 ; Kuznetsov & Kazansky, 2008 ), biologically active compounds with a wide range efficiency (Chohan et al., 2010 ) and as high-energy compounds (Kofman, 2002 ). The present work report the synthesis and crystal structure of the title compound (Fig. 1).

Figure 1
Plot of the constituents of the title compound, showing the atom-labelling scheme. Displacement ellipsoids are drawn at the 50% probability level.

The asymmetric unit comprises a 3,5-diamino-4H-1,2,4-triazol-1-ium cation, a 4-nitrobenzoate anion and two water molecules The maximum deviation from the mean plane of the triazolyl ring is 0.003 (1) Å. Small twists are noted in the anion with the dihedral angles between the ring and carboxylate and nitro groups being 7.82 (13) and 9.10 (15)°, respectively. A similar structure has been reported previously (Ren et al., 2013 ) isolated from the reaction of 3,5-dinitrobenzoic acid and 3,5-diamino-1,2,4-triazole.

In the crystal, the cations and anions are interconnected and are connected to the water molecules by N—H⋯O, N—H⋯N and O—H⋯O strong hydrogen bonds to form sheets parallel to ( $[\overline{1}]$ 01); C—H⋯O interactions are also noted. In addition, the layers are linked by O—H⋯O hydrogen bonds and π–π interactions between triazolyl and benzoate rings [inter-centroid distance = 3.4967 (8) Å], forming a three-dimensional network as shown in Fig. 2 and Table 1.

Table 1
Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
N2—H2N⋯O3	0.97	1.76	2.7221 (14)	176
N3—H3N⋯O5	0.94	1.86	2.8021 (16)	176
N5—H5B⋯O4	0.87	1.93	2.7871 (17)	170
N6—H6A⋯O6	0.85	2.34	3.1866 (19)	174
N6—H6B⋯O5ⁱ	0.85	2.29	3.1318 (17)	170
N5—H5A⋯N4ⁱⁱ	0.90	2.06	2.9224 (17)	159
O5—H5AO⋯O6ⁱⁱⁱ	0.88	1.95	2.8156 (18)	166
O5—H5BO⋯O4ⁱ	0.87	1.92	2.7868 (16)	176
O6—H6AO⋯O3	0.92	1.87	2.7363 (15)	157
O6—H6BO⋯O4^iv	0.92	2.24	3.0419 (19)	146
C6—H6⋯O2^v	0.93	2.45	3.333 (2)	160
Symmetry codes: (i) $[x-{\script{1\over 2}}, -y+{\script{1\over 2}}, z-{\script{1\over 2}}]$ ; (ii) $[x+{\script{1\over 2}}, -y+{\script{1\over 2}}, z+{\script{1\over 2}}]$ ; (iii) $[-x+{\script{1\over 2}}, y-{\script{1\over 2}}, -z+{\script{1\over 2}}]$ ; (iv) -x, -y+1, -z+1; (v) $[x-{\script{1\over 2}}, -y+{\script{3\over 2}}, z-{\script{1\over 2}}]$ .

Figure 2
Partial crystal packing for the title compound, showing molecules linked by N—H⋯O and O—H⋯O hydrogen bonds and by π–π interactions, forming a three-dimensional network.

Synthesis and crystallization

A mixture of 3,5-diamino-1,2,4 triazole (0.50 g; 5 mmol), 4-nitrobenzoyl chloride (0.92 g; 5 mmol) in ethanol-water solution (30 ml) was heated at reflux for 12 h. The completion of the reaction was confirmed by TLC. The solvent was removed by evaporation and the residue was recrystallized from ethanol solution to afford the title salt as colourless crystals.

Refinement

Crystal data, data collection and structure refinement details are summarized in Table 2.

Table 2
Experimental details

Crystal data
Chemical formula	C₂H₆N₅⁺·C₇H₄NO₄⁻·2H₂O
M_r	302.26
Crystal system, space group	Monoclinic, P2₁/n
Temperature (K)	296
a, b, c (Å)	7.2050 (2), 19.8831 (6), 9.7676 (3)
β (°)	105.691 (1)
V (Å³)	1347.14 (7)
Z	4
Radiation type	Mo Kα
μ (mm⁻¹)	0.13
Crystal size (mm)	0.37 × 0.32 × 0.27

Data collection
Diffractometer	Bruker X8 APEX
Absorption correction	Multi-scan (SADABS; Krause et al., 2015 )
T_min, T_max	0.645, 0.746
No. of measured, independent and observed [I > 2σ(I)] reflections	24987, 3487, 2811
R_int	0.028
(sin θ/λ)_max (Å⁻¹)	0.676

Refinement
R[F² > 2σ(F²)], wR(F²), S	0.043, 0.133, 1.05
No. of reflections	3487
No. of parameters	190
H-atom treatment	H-atom parameters constrained
Δρ_max, Δρ_min (e Å⁻³)	0.34, −0.23
Computer programs: APEX2 and SAINT (Bruker, 2009 ), SHELXTL2014 (Sheldrick, 2015a ), SHELXL2014 (Sheldrick, 2015b ), ORTEP-3 for Windows (Farrugia, 2012 ), Mercury (Macrae et al., 2008 ) and publCIF (Westrip, 2010 ).

Structural data

CCDC reference: 1530351

Crystal structure: contains datablock I. DOI: https://doi.org/10.1107/S2414314617001596/tk4030sup1.cif

Structure factors: contains datablock I. DOI: https://doi.org/10.1107/S2414314617001596/tk4030Isup2.hkl

Supporting information file. DOI: https://doi.org/10.1107/S2414314617001596/tk4030Isup3.cml

checkCIF report

Computing details top

Data collection: APEX2 (Bruker, 2009); cell refinement: SAINT (Bruker, 2009); data reduction: SAINT (Bruker, 2009); program(s) used to solve structure: SHELXTL2014 (Sheldrick, 2015a); program(s) used to refine structure: SHELXL2014 (Sheldrick, 2015b); molecular graphics: ORTEP-3 for Windows (Farrugia, 2012); software used to prepare material for publication: Mercury (Macrae et al., 2008) and publCIF (Westrip, 2010).

3,5-Diamino-4H-1,2,4-triazol-1-ium 4-nitrobenzoate dihydrate top

Crystal data top

C₂H₆N₅⁺·C₇H₄NO₄⁻·2H₂O	F(000) = 632
M_r = 302.26	D_x = 1.490 Mg m⁻³
Monoclinic, P2₁/n	Mo Kα radiation, λ = 0.71073 Å
a = 7.2050 (2) Å	Cell parameters from 3487 reflections
b = 19.8831 (6) Å	θ = 2.4–28.7°
c = 9.7676 (3) Å	µ = 0.13 mm⁻¹
β = 105.691 (1)°	T = 296 K
V = 1347.14 (7) Å³	Block, colourless
Z = 4	0.37 × 0.32 × 0.27 mm

Data collection top

Bruker X8 APEX diffractometer	3487 independent reflections
Radiation source: fine-focus sealed tube	2811 reflections with I > 2σ(I)
Graphite monochromator	R_int = 0.028
φ and ω scans	θ_max = 28.7°, θ_min = 2.4°
Absorption correction: multi-scan (SADABS; Krause et al., 2015)	h = −9→9
T_min = 0.645, T_max = 0.746	k = −26→26
24987 measured reflections	l = −13→12

Refinement top

Refinement on F²	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F² > 2σ(F²)] = 0.043	H-atom parameters constrained
wR(F²) = 0.133	w = 1/[σ²(F_o²) + (0.068P)² + 0.370P] where P = (F_o² + 2F_c²)/3
S = 1.05	(Δ/σ)_max = 0.001
3487 reflections	Δρ_max = 0.34 e Å⁻³
190 parameters	Δρ_min = −0.23 e Å⁻³

Special details top

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

Fractional atomic coordinates and isotropic or equivalent isotropic displacement parameters (Å²) top

	x	y	z	U_iso*/U_eq
C1	0.5653 (2)	0.65186 (7)	0.88659 (15)	0.0402 (3)
C2	0.6168 (2)	0.58783 (7)	0.93513 (15)	0.0436 (3)
H2	0.6969	0.5804	1.0259	0.052*
C3	0.5457 (2)	0.53473 (7)	0.84470 (14)	0.0395 (3)
H3	0.5783	0.4909	0.8752	0.047*
C4	0.42631 (18)	0.54581 (6)	0.70904 (13)	0.0313 (3)
C5	0.3781 (2)	0.61125 (6)	0.66323 (15)	0.0378 (3)
H5	0.2987	0.6190	0.5723	0.045*
C6	0.4482 (2)	0.66517 (7)	0.75320 (17)	0.0424 (3)
H6	0.4166	0.7092	0.7237	0.051*
C7	0.34457 (19)	0.48612 (6)	0.61666 (14)	0.0349 (3)
C8	0.1939 (2)	0.32045 (6)	0.39199 (14)	0.0370 (3)
C9	0.02010 (18)	0.37170 (7)	0.20317 (14)	0.0350 (3)
N1	0.6422 (2)	0.70814 (7)	0.98345 (16)	0.0554 (4)
N2	0.12815 (16)	0.38183 (5)	0.34091 (12)	0.0352 (2)
H2N	0.1630	0.4232	0.3935	0.042*
N3	0.12583 (18)	0.27665 (6)	0.28955 (13)	0.0419 (3)
H3N	0.1470	0.2300	0.2980	0.050*
N4	0.01422 (18)	0.30828 (6)	0.16723 (13)	0.0415 (3)
N5	0.3061 (2)	0.30868 (6)	0.52092 (14)	0.0546 (4)
H5A	0.3503	0.2672	0.5476	0.066*
H5B	0.3371	0.3434	0.5763	0.066*
N6	−0.0649 (2)	0.42254 (7)	0.11816 (14)	0.0478 (3)
H6A	−0.0507	0.4620	0.1533	0.057*
H6B	−0.1362	0.4100	0.0385	0.057*
O1	0.6188 (2)	0.76516 (6)	0.93599 (18)	0.0773 (4)
O2	0.7257 (3)	0.69499 (8)	1.10651 (16)	0.0888 (5)
O3	0.24541 (16)	0.49644 (5)	0.49201 (11)	0.0478 (3)
O4	0.37626 (18)	0.42890 (5)	0.67293 (12)	0.0518 (3)
O5	0.20562 (17)	0.13888 (5)	0.32618 (12)	0.0516 (3)
H5AO	0.3003	0.1230	0.2943	0.077*
H5BO	0.1041	0.1162	0.2822	0.077*
O6	0.01665 (19)	0.56608 (6)	0.26751 (13)	0.0589 (3)
H6AO	0.0886	0.5529	0.3562	0.088*
H6BO	−0.0927	0.5865	0.2780	0.088*

Atomic displacement parameters (Å²) top

	U¹¹	U²²	U³³	U¹²	U¹³	U²³
C1	0.0440 (7)	0.0333 (6)	0.0431 (7)	−0.0053 (5)	0.0115 (6)	−0.0109 (5)
C2	0.0512 (8)	0.0400 (7)	0.0337 (7)	−0.0024 (6)	0.0014 (6)	−0.0045 (5)
C3	0.0489 (8)	0.0293 (6)	0.0352 (6)	0.0010 (5)	0.0025 (6)	0.0009 (5)
C4	0.0340 (6)	0.0265 (5)	0.0316 (6)	−0.0020 (4)	0.0059 (5)	−0.0007 (4)
C5	0.0413 (7)	0.0289 (6)	0.0384 (7)	0.0011 (5)	0.0028 (5)	0.0032 (5)
C6	0.0482 (8)	0.0251 (6)	0.0516 (8)	0.0019 (5)	0.0098 (6)	0.0001 (5)
C7	0.0377 (6)	0.0275 (6)	0.0352 (6)	−0.0012 (5)	0.0024 (5)	−0.0006 (5)
C8	0.0405 (7)	0.0269 (6)	0.0384 (7)	−0.0021 (5)	0.0017 (5)	−0.0006 (5)
C9	0.0320 (6)	0.0342 (6)	0.0352 (6)	−0.0006 (5)	0.0026 (5)	−0.0027 (5)
N1	0.0634 (9)	0.0411 (7)	0.0603 (9)	−0.0095 (6)	0.0143 (7)	−0.0194 (6)
N2	0.0386 (6)	0.0265 (5)	0.0345 (6)	0.0001 (4)	−0.0004 (4)	−0.0021 (4)
N3	0.0489 (7)	0.0265 (5)	0.0426 (6)	−0.0020 (5)	−0.0006 (5)	−0.0032 (4)
N4	0.0441 (6)	0.0338 (6)	0.0387 (6)	−0.0017 (5)	−0.0021 (5)	−0.0041 (5)
N5	0.0730 (9)	0.0319 (6)	0.0425 (7)	0.0040 (6)	−0.0126 (6)	0.0009 (5)
N6	0.0533 (7)	0.0404 (6)	0.0399 (6)	0.0080 (5)	−0.0045 (5)	0.0004 (5)
O1	0.0944 (11)	0.0375 (6)	0.0920 (10)	−0.0042 (6)	0.0115 (8)	−0.0217 (7)
O2	0.1303 (14)	0.0664 (9)	0.0536 (8)	−0.0222 (9)	−0.0027 (8)	−0.0234 (7)
O3	0.0591 (6)	0.0337 (5)	0.0373 (5)	0.0006 (4)	−0.0096 (5)	−0.0014 (4)
O4	0.0699 (7)	0.0267 (5)	0.0455 (6)	−0.0028 (4)	−0.0074 (5)	0.0024 (4)
O5	0.0571 (7)	0.0361 (5)	0.0538 (6)	−0.0023 (5)	0.0018 (5)	−0.0070 (4)
O6	0.0613 (7)	0.0595 (7)	0.0495 (6)	0.0077 (6)	0.0041 (5)	0.0136 (5)

Geometric parameters (Å, º) top

C1—C6	1.373 (2)	C9—N4	1.3065 (17)
C1—C2	1.374 (2)	C9—N6	1.3459 (18)
C1—N1	1.4734 (18)	C9—N2	1.3748 (16)
C2—C3	1.3831 (19)	N1—O1	1.219 (2)
C2—H2	0.9300	N1—O2	1.218 (2)
C3—C4	1.3884 (18)	N2—H2N	0.9671
C3—H3	0.9300	N3—N4	1.3964 (17)
C4—C5	1.3891 (17)	N3—H3N	0.9397
C4—C7	1.5107 (17)	N5—H5A	0.8975
C5—C6	1.3918 (19)	N5—H5B	0.8689
C5—H5	0.9300	N6—H6A	0.8520
C6—H6	0.9300	N6—H6B	0.8459
C7—O3	1.2508 (16)	O5—H5AO	0.8816
C7—O4	1.2573 (16)	O5—H5BO	0.8682
C8—N3	1.3170 (17)	O6—H6AO	0.9193
C8—N5	1.3203 (18)	O6—H6BO	0.9165
C8—N2	1.3548 (16)

C6—C1—C2	123.04 (13)	N5—C8—N2	125.02 (12)
C6—C1—N1	119.40 (13)	N4—C9—N6	125.65 (12)
C2—C1—N1	117.56 (13)	N4—C9—N2	111.90 (12)
C1—C2—C3	117.91 (13)	N6—C9—N2	122.44 (12)
C1—C2—H2	121.0	O1—N1—O2	123.74 (15)
C3—C2—H2	121.0	O1—N1—C1	118.22 (15)
C2—C3—C4	121.01 (13)	O2—N1—C1	118.04 (14)
C2—C3—H3	119.5	C8—N2—C9	106.10 (10)
C4—C3—H3	119.5	C8—N2—H2N	123.8
C3—C4—C5	119.51 (11)	C9—N2—H2N	129.9
C3—C4—C7	119.09 (11)	C8—N3—N4	111.24 (11)
C5—C4—C7	121.35 (11)	C8—N3—H3N	124.5
C4—C5—C6	120.10 (12)	N4—N3—H3N	124.2
C4—C5—H5	119.9	C9—N4—N3	103.62 (11)
C6—C5—H5	119.9	C8—N5—H5A	121.2
C1—C6—C5	118.42 (12)	C8—N5—H5B	116.2
C1—C6—H6	120.8	H5A—N5—H5B	122.6
C5—C6—H6	120.8	C9—N6—H6A	117.3
O3—C7—O4	124.21 (12)	C9—N6—H6B	114.1
O3—C7—C4	118.71 (11)	H6A—N6—H6B	128.3
O4—C7—C4	117.03 (11)	H5AO—O5—H5BO	105.6
N3—C8—N5	127.85 (13)	H6AO—O6—H6BO	107.7
N3—C8—N2	107.13 (11)

Hydrogen-bond geometry (Å, º) top

D—H···A	D—H	H···A	D···A	D—H···A
N2—H2N···O3	0.97	1.76	2.7221 (14)	176
N3—H3N···O5	0.94	1.86	2.8021 (16)	176
N5—H5B···O4	0.87	1.93	2.7871 (17)	170
N6—H6A···O6	0.85	2.34	3.1866 (19)	174
N6—H6B···O5ⁱ	0.85	2.29	3.1318 (17)	170
N5—H5A···N4ⁱⁱ	0.90	2.06	2.9224 (17)	159
O5—H5AO···O6ⁱⁱⁱ	0.88	1.95	2.8156 (18)	166
O5—H5BO···O4ⁱ	0.87	1.92	2.7868 (16)	176
O6—H6AO···O3	0.92	1.87	2.7363 (15)	157
O6—H6BO···O4^iv	0.92	2.24	3.0419 (19)	146
C6—H6···O2^v	0.93	2.45	3.333 (2)	160

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

Acknowledgements

The authors thank the Unit of Support for Technical and Scientific Research (UATRS, CNRST) for the X-ray measurements and the Mohammed V University in Rabat, for financial support.

References

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