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

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.

Key indicators

• Single-crystal X-ray study
• T = 296 K
• Mean [sigma](C-C) = 0.002 Å
• R factor = 0.043
• wR factor = 0.133
• Data-to-parameter ratio = 18.4

checkCIF/PLATON results

No syntax errors found



Alert level C
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.3 Note
PLAT250_ALERT_2_C Large U3/U1 Ratio for Average U(i,j) Tensor ....        2.1 Note
PLAT905_ALERT_3_C Negative K value in the Analysis of Variance ...     -0.488 Report

Alert level G
PLAT007_ALERT_5_G Number of Unrefined Donor-H Atoms ..............         10 Report
PLAT042_ALERT_1_G Calc. and Reported MoietyFormula Strings  Differ     Please Check
PLAT720_ALERT_4_G Number of Unusual/Non-Standard Labels ..........          4 Note
PLAT910_ALERT_3_G Missing # of FCF Reflection(s) Below Theta(Min)           1 Note
PLAT913_ALERT_3_G Missing # of Very Strong Reflections in FCF ....          1 Note
PLAT933_ALERT_2_G Number of OMIT Records in Embedded .res File ...          1 Note
PLAT978_ALERT_2_G Number C-C Bonds with Positive Residual Density.          6 Note

   0 ALERT level A = Most likely a serious problem - resolve or explain
   0 ALERT level B = A potentially serious problem, consider carefully
   3 ALERT level C = Check. Ensure it is not caused by an omission or oversight
   7 ALERT level G = General information/check it is not something unexpected

   1 ALERT type 1 CIF construction/syntax error, inconsistent or missing data
   4 ALERT type 2 Indicator that the structure model may be wrong or deficient
   3 ALERT type 3 Indicator that the structure quality may be low
   1 ALERT type 4 Improvement, methodology, query or suggestion
   1 ALERT type 5 Informative message, check

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Computing details

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

Crystal data

C2H6N5^+·C7H4NO4^−·2H2O	F(000) = 632
Mr = 302.26	Dx = 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) Å^3	Block, colourless
Z = 4	0.37 × 0.32 × 0.27 mm

Data collection

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

Refinement

Refinement on F^2	0 restraints
Least-squares matrix: full	Hydrogen site location: mixed
R[F^2 > 2σ(F^2)] = 0.043	H-atom parameters constrained
wR(F^2) = 0.133	w = 1/[σ^2(Fo^2) + (0.068P)^2 + 0.370P] where P = (Fo^2 + 2Fc^2)/3
S = 1.05	(Δ/σ)max = 0.001
3487 reflections	Δρmax = 0.34 e Å^−3
190 parameters	Δρmin = −0.23 e Å^−3

Special details

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 (Ų)

	x	y	z	Uiso*/Ueq
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 (Ų)

	U^11	U^22	U^33	U^12	U^13	U^23
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)

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)

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···O5^i	0.85	2.29	3.1318 (17)	170
N5—H5A···N4^ii	0.90	2.06	2.9224 (17)	159
O5—H5AO···O6^iii	0.88	1.95	2.8156 (18)	166
O5—H5BO···O4^i	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.