Ethane-1,2-diaminium bis-{5-[4-(1H-tetra-zol-5-yl)phen-yl]tetra-zolide} dihydrate.

In the two anions of the title salt, C(2)H(10)N(2) (2+)·2C(8)H(5)N(8) (-)·2H(2)O, the central aromatic rings make dihedral angles of 13.53 (6) and 6.53 (7)° with the deprotonated tetra-zole rings, and 11.39 (6) and 10.41 (9)° with the other tetra-zole groups. In the crystal, the cations, anions and water mol-ecules are linked by an extensive O-H⋯N, N-H⋯O and N-H⋯N hydrogen-bond network into two-dimensional wave-like duplex sheets extending parallel to the bc plane. π-π stacking inter-actions between benzene rings [inter-centroid distances are 3.8482 (4) and 3.9621 (5) Å] and between tetra-zole rings [inter-centroid distances are 3.4350 (4) and 3.7169 (4) Å] further consolidate the crystal structure.

Related literature

For similar structures, see: Tao et al. (2004 ▶); Deng et al. (2010 ▶); He et al. (2008 ▶). For 5,5′-(1,4-phenyl­ene)bis­(1H-tetra­zole) applied in coordination chemistry, see: Liu et al. (2010 ▶); Ouellette et al. (2009 ▶); Dinca et al. (2006 ▶); Qiao et al. (2011 ▶).

Experimental

Crystal data

C2H10N2 2+·2C8H5N8 −·2H2O

M = 524.55

Triclinic,

a = 7.3918 (9) Å

b = 12.4699 (16) Å

c = 13.6367 (17) Å

α = 89.774 (2)°

β = 78.556 (2)°

γ = 74.153 (2)°

V = 1183.5 (3) Å3

Z = 2

Mo Kα radiation

μ = 0.11 mm−1

T = 296 K

0.32 × 0.28 × 0.11 mm

Data collection

Bruker APEXII CCD diffractometer

Absorption correction: multi-scan (SADABS; Bruker, 2008 ▶) T min = 0.966, T max = 0.988

5924 measured reflections

4089 independent reflections

3254 reflections with I > 2σ(I)

R int = 0.017

Refinement

R[F 2 > 2σ(F 2)] = 0.042

wR(F 2) = 0.122

S = 1.02

4089 reflections

345 parameters

H-atom parameters constrained

Δρmax = 0.19 e Å−3

Δρmin = −0.23 e Å−3

Data collection: APEX2 (Bruker, 2008 ▶); cell refinement: SAINT (Bruker, 2008 ▶); data reduction: SAINT; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: ORTEP-3 (Farrugia, 1997 ▶); software used to prepare material for publication: SHELXL97.

Crystal structure: contains datablock(s) global, I. DOI: 10.1107/S1600536811034143/yk2016sup1.cif

Structure factors: contains datablock(s) I. DOI: 10.1107/S1600536811034143/yk2016Isup2.hkl

Supplementary material file. DOI: 10.1107/S1600536811034143/yk2016Isup3.cml

Additional supplementary materials: crystallographic information; 3D view; checkCIF report

C2H10N22+·2C8H5N8−·2H2O	Z = 2
Mr = 524.55	F(000) = 548
Triclinic, P1	Dx = 1.472 Mg m−3Dm = 1.472 Mg m−3Dm measured by not measured
Hall symbol: -P 1	Mo Kα radiation, λ = 0.71073 Å
a = 7.3918 (9) Å	Cell parameters from 2314 reflections
b = 12.4699 (16) Å	θ = 2.9–25.8°
c = 13.6367 (17) Å	µ = 0.11 mm−1
α = 89.774 (2)°	T = 296 K
β = 78.556 (2)°	Block, colorless
γ = 74.153 (2)°	0.32 × 0.28 × 0.11 mm
V = 1183.5 (3) Å3

Bruker APEXII CCD diffractometer	4089 independent reflections
Radiation source: fine-focus sealed tube	3254 reflections with I > 2σ(I)
graphite	Rint = 0.017
φ and ω scans	θmax = 25.0°, θmin = 1.5°
Absorption correction: multi-scan (SADABS; Bruker, 2008)	h = −8→8
Tmin = 0.966, Tmax = 0.988	k = −14→11
5924 measured reflections	l = −16→16

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)] = 0.042	Hydrogen site location: inferred from neighbouring sites
wR(F2) = 0.122	H-atom parameters constrained
S = 1.02	w = 1/[σ2(Fo2) + (0.0641P)2 + 0.2582P] where P = (Fo2 + 2Fc2)/3
4089 reflections	(Δ/σ)max < 0.001
345 parameters	Δρmax = 0.19 e Å−3
0 restraints	Δρmin = −0.23 e Å−3

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

	x	y	z	Uiso*/Ueq
C11A	0.2135 (2)	0.47786 (13)	0.31175 (12)	0.0301 (4)
C12A	0.2209 (2)	0.37261 (13)	0.26227 (12)	0.0297 (4)
C13A	0.2551 (3)	0.36244 (14)	0.15792 (12)	0.0333 (4)
H13A	0.2671	0.4237	0.1207	0.040*
C14A	0.2017 (3)	0.28026 (14)	0.31627 (13)	0.0367 (4)
H14A	0.1790	0.2857	0.3859	0.044*
C11B	0.2752 (3)	0.96745 (14)	0.60365 (12)	0.0333 (4)
C12B	0.2807 (3)	0.86208 (14)	0.65171 (12)	0.0321 (4)
C13B	0.2756 (3)	0.85759 (14)	0.75418 (13)	0.0352 (4)
H13B	0.2664	0.9219	0.7914	0.042*
C14B	0.2936 (3)	0.76531 (15)	0.59755 (13)	0.0394 (5)
H14B	0.2969	0.7672	0.5290	0.047*
C9	0.0711 (3)	0.20961 (15)	0.83423 (13)	0.0378 (4)
H9A	0.0183	0.1467	0.8323	0.045*
H9B	0.0523	0.2512	0.7751	0.045*
C10	−0.0329 (3)	0.28374 (15)	0.92698 (13)	0.0370 (4)
H10A	−0.0148	0.2421	0.9862	0.044*
H10B	0.0201	0.3466	0.9290	0.044*
C1A	0.2689 (2)	0.06357 (13)	0.11169 (12)	0.0285 (4)
C2A	0.2516 (2)	0.16970 (13)	0.16380 (12)	0.0289 (4)
C3A	0.2159 (3)	0.18057 (14)	0.26764 (13)	0.0357 (4)
H3A	0.2012	0.1198	0.3050	0.043*
C4A	0.2713 (3)	0.26267 (14)	0.10956 (12)	0.0325 (4)
H4A	0.2956	0.2570	0.0399	0.039*
C1B	0.3137 (2)	0.55566 (14)	0.79614 (12)	0.0294 (4)
C2B	0.2975 (2)	0.66181 (14)	0.74691 (12)	0.0308 (4)
C3B	0.3016 (3)	0.66656 (15)	0.64432 (13)	0.0391 (4)
H3B	0.3099	0.6024	0.6071	0.047*
C4B	0.2841 (3)	0.75917 (14)	0.80075 (12)	0.0343 (4)
H4B	0.2808	0.7575	0.8693	0.041*
N11A	0.2160 (2)	0.49535 (11)	0.40801 (10)	0.0373 (4)
H11A	0.2204	0.4457	0.4521	0.045*
N12A	0.2104 (3)	0.60166 (12)	0.42518 (11)	0.0446 (4)
N13A	0.2043 (3)	0.64840 (12)	0.34094 (11)	0.0426 (4)
N14A	0.2065 (2)	0.57367 (12)	0.26830 (10)	0.0355 (4)
N11B	0.2501 (3)	0.98954 (12)	0.51052 (11)	0.0436 (4)
H11B	0.2368	0.9431	0.4679	0.052*
N12B	0.2491 (3)	1.09568 (13)	0.49410 (12)	0.0527 (5)
N13B	0.2731 (3)	1.13653 (13)	0.57554 (12)	0.0506 (5)
N14B	0.2906 (3)	1.05895 (12)	0.64532 (11)	0.0417 (4)
N9	0.2778 (2)	0.16876 (11)	0.83363 (10)	0.0322 (3)
H9C	0.3286	0.2261	0.8290	0.048*
H9D	0.3353	0.1206	0.7815	0.048*
H9E	0.2945	0.1350	0.8901	0.048*
N10	−0.2399 (2)	0.32474 (11)	0.92681 (10)	0.0315 (3)
H10C	−0.2562	0.3631	0.8726	0.047*
H10D	−0.2994	0.3688	0.9814	0.047*
H10E	−0.2888	0.2670	0.9263	0.047*
N1A	0.2669 (2)	0.05241 (11)	0.01421 (10)	0.0339 (4)
N2A	0.2887 (2)	−0.05668 (12)	−0.00421 (11)	0.0381 (4)
N3A	0.3040 (2)	−0.10827 (12)	0.07894 (11)	0.0392 (4)
N4A	0.2908 (2)	−0.03469 (12)	0.15402 (10)	0.0351 (4)
N1B	0.3320 (2)	0.54178 (11)	0.89155 (10)	0.0346 (4)
N2B	0.3495 (2)	0.43315 (12)	0.90616 (11)	0.0385 (4)
N3B	0.3432 (2)	0.38426 (12)	0.82212 (11)	0.0404 (4)
N4B	0.3198 (2)	0.45938 (12)	0.75156 (11)	0.0376 (4)
O1	0.2556 (2)	0.37535 (11)	0.57068 (10)	0.0567 (4)
H1B	0.2661	0.3062	0.5750	0.085*
H1A	0.2766	0.4000	0.6234	0.085*
O2	0.2347 (3)	0.87668 (13)	0.34653 (11)	0.0842 (7)
H2A	0.2303	0.8101	0.3399	0.126*
H2B	0.2537	0.9038	0.2915	0.126*

	U11	U22	U33	U12	U13	U23
C11A	0.0383 (10)	0.0262 (9)	0.0257 (8)	−0.0075 (7)	−0.0084 (7)	0.0014 (7)
C12A	0.0370 (10)	0.0251 (9)	0.0269 (9)	−0.0077 (7)	−0.0081 (7)	0.0007 (7)
C13A	0.0496 (11)	0.0261 (9)	0.0284 (9)	−0.0146 (8)	−0.0120 (8)	0.0040 (7)
C14A	0.0569 (12)	0.0319 (10)	0.0227 (8)	−0.0146 (8)	−0.0084 (8)	0.0012 (7)
C11B	0.0463 (11)	0.0281 (9)	0.0252 (9)	−0.0100 (8)	−0.0069 (7)	0.0005 (7)
C12B	0.0423 (11)	0.0261 (9)	0.0287 (9)	−0.0099 (7)	−0.0087 (7)	0.0024 (7)
C13B	0.0513 (12)	0.0265 (9)	0.0292 (9)	−0.0122 (8)	−0.0096 (8)	0.0003 (7)
C14B	0.0643 (13)	0.0319 (10)	0.0253 (9)	−0.0141 (9)	−0.0157 (8)	0.0038 (7)
C9	0.0398 (11)	0.0394 (10)	0.0331 (10)	−0.0069 (8)	−0.0104 (8)	−0.0061 (8)
C10	0.0381 (11)	0.0406 (10)	0.0323 (9)	−0.0104 (8)	−0.0083 (8)	−0.0046 (8)
C1A	0.0347 (10)	0.0261 (9)	0.0266 (8)	−0.0115 (7)	−0.0069 (7)	0.0029 (7)
C2A	0.0351 (10)	0.0244 (8)	0.0292 (9)	−0.0092 (7)	−0.0099 (7)	0.0010 (7)
C3A	0.0563 (12)	0.0252 (9)	0.0284 (9)	−0.0167 (8)	−0.0077 (8)	0.0050 (7)
C4A	0.0459 (11)	0.0307 (9)	0.0240 (8)	−0.0135 (8)	−0.0103 (7)	0.0029 (7)
C1B	0.0352 (10)	0.0272 (9)	0.0279 (9)	−0.0107 (7)	−0.0083 (7)	0.0014 (7)
C2B	0.0368 (10)	0.0292 (9)	0.0279 (9)	−0.0109 (7)	−0.0081 (7)	0.0020 (7)
C3B	0.0630 (13)	0.0266 (9)	0.0304 (9)	−0.0137 (9)	−0.0142 (9)	−0.0006 (7)
C4B	0.0496 (11)	0.0312 (9)	0.0230 (8)	−0.0126 (8)	−0.0074 (8)	0.0014 (7)
N11A	0.0625 (11)	0.0240 (8)	0.0287 (8)	−0.0130 (7)	−0.0160 (7)	0.0025 (6)
N12A	0.0762 (12)	0.0290 (8)	0.0331 (8)	−0.0175 (8)	−0.0179 (8)	0.0004 (7)
N13A	0.0665 (12)	0.0287 (8)	0.0354 (9)	−0.0157 (7)	−0.0134 (8)	−0.0017 (7)
N14A	0.0526 (10)	0.0267 (8)	0.0292 (8)	−0.0123 (7)	−0.0116 (7)	0.0017 (6)
N11B	0.0780 (13)	0.0284 (8)	0.0289 (8)	−0.0186 (8)	−0.0163 (8)	0.0032 (6)
N12B	0.0961 (15)	0.0315 (9)	0.0346 (9)	−0.0219 (9)	−0.0170 (9)	0.0077 (7)
N13B	0.0888 (14)	0.0299 (9)	0.0341 (9)	−0.0189 (9)	−0.0116 (9)	0.0036 (7)
N14B	0.0689 (12)	0.0283 (8)	0.0296 (8)	−0.0165 (7)	−0.0098 (7)	0.0032 (6)
N9	0.0397 (9)	0.0283 (8)	0.0284 (7)	−0.0087 (6)	−0.0074 (6)	−0.0002 (6)
N10	0.0387 (9)	0.0260 (7)	0.0297 (8)	−0.0083 (6)	−0.0078 (6)	0.0008 (6)
N1A	0.0479 (9)	0.0276 (8)	0.0287 (8)	−0.0122 (7)	−0.0111 (7)	0.0003 (6)
N2A	0.0535 (10)	0.0304 (8)	0.0324 (8)	−0.0151 (7)	−0.0086 (7)	−0.0019 (6)
N3A	0.0553 (10)	0.0283 (8)	0.0365 (9)	−0.0177 (7)	−0.0064 (7)	−0.0013 (7)
N4A	0.0505 (10)	0.0274 (8)	0.0303 (8)	−0.0153 (7)	−0.0083 (7)	0.0024 (6)
N1B	0.0485 (10)	0.0287 (8)	0.0281 (8)	−0.0123 (7)	−0.0092 (7)	0.0045 (6)
N2B	0.0539 (10)	0.0309 (8)	0.0347 (8)	−0.0161 (7)	−0.0122 (7)	0.0074 (6)
N3B	0.0562 (10)	0.0301 (8)	0.0379 (9)	−0.0161 (7)	−0.0106 (7)	0.0042 (7)
N4B	0.0576 (10)	0.0281 (8)	0.0320 (8)	−0.0170 (7)	−0.0135 (7)	0.0039 (6)
O1	0.1072 (13)	0.0371 (8)	0.0373 (7)	−0.0283 (8)	−0.0303 (8)	0.0085 (6)
O2	0.190 (2)	0.0513 (10)	0.0361 (8)	−0.0628 (12)	−0.0398 (11)	0.0109 (7)

C11A—N14A	1.324 (2)	C1B—N4B	1.334 (2)
C11A—N11A	1.336 (2)	C1B—N1B	1.340 (2)
C11A—C12A	1.461 (2)	C1B—C2B	1.468 (2)
C12A—C14A	1.389 (2)	C2B—C4B	1.391 (2)
C12A—C13A	1.395 (2)	C2B—C3B	1.395 (2)
C13A—C4A	1.375 (2)	C3B—H3B	0.9300
C13A—H13A	0.9300	C4B—H4B	0.9300
C14A—C3A	1.380 (2)	N11A—N12A	1.335 (2)
C14A—H14A	0.9300	N11A—H11A	0.8600
C11B—N14B	1.319 (2)	N12A—N13A	1.289 (2)
C11B—N11B	1.336 (2)	N13A—N14A	1.3574 (19)
C11B—C12B	1.460 (2)	N11B—N12B	1.340 (2)
C12B—C14B	1.388 (2)	N11B—H11B	0.8600
C12B—C13B	1.392 (2)	N12B—N13B	1.287 (2)
C13B—C4B	1.372 (2)	N13B—N14B	1.353 (2)
C13B—H13B	0.9300	N9—H9C	0.8900
C14B—C3B	1.377 (2)	N9—H9D	0.8900
C14B—H14B	0.9300	N9—H9E	0.8900
C9—N9	1.471 (2)	N10—H10C	0.8900
C9—C10	1.510 (2)	N10—H10D	0.8900
C9—H9A	0.9700	N10—H10E	0.8900
C9—H9B	0.9700	N1A—N2A	1.3440 (19)
C10—N10	1.475 (2)	N2A—N3A	1.311 (2)
C10—H10A	0.9700	N3A—N4A	1.349 (2)
C10—H10B	0.9700	N1B—N2B	1.3430 (19)
C1A—N4A	1.336 (2)	N2B—N3B	1.315 (2)
C1A—N1A	1.340 (2)	N3B—N4B	1.3431 (19)
C1A—C2A	1.467 (2)	O1—H1B	0.8477
C2A—C3A	1.388 (2)	O1—H1A	0.8408
C2A—C4A	1.398 (2)	O2—H2A	0.8464
C3A—H3A	0.9300	O2—H2B	0.8243
C4A—H4A	0.9300
N14A—C11A—N11A	107.27 (14)	C2A—C4A—H4A	119.6
N14A—C11A—C12A	125.89 (14)	N4B—C1B—N1B	110.77 (14)
N11A—C11A—C12A	126.82 (15)	N4B—C1B—C2B	124.99 (14)
C14A—C12A—C13A	118.65 (15)	N1B—C1B—C2B	124.19 (15)
C14A—C12A—C11A	121.72 (15)	C4B—C2B—C3B	118.44 (15)
C13A—C12A—C11A	119.58 (14)	C4B—C2B—C1B	120.84 (15)
C4A—C13A—C12A	120.61 (15)	C3B—C2B—C1B	120.68 (15)
C4A—C13A—H13A	119.7	C14B—C3B—C2B	120.64 (16)
C12A—C13A—H13A	119.7	C14B—C3B—H3B	119.7
C3A—C14A—C12A	120.65 (16)	C2B—C3B—H3B	119.7
C3A—C14A—H14A	119.7	C13B—C4B—C2B	120.90 (15)
C12A—C14A—H14A	119.7	C13B—C4B—H4B	119.5
N14B—C11B—N11B	107.58 (15)	C2B—C4B—H4B	119.5
N14B—C11B—C12B	125.96 (15)	N12A—N11A—C11A	109.55 (14)
N11B—C11B—C12B	126.46 (15)	N12A—N11A—H11A	125.2
C14B—C12B—C13B	118.83 (15)	C11A—N11A—H11A	125.2
C14B—C12B—C11B	121.69 (15)	N13A—N12A—N11A	106.35 (14)
C13B—C12B—C11B	119.47 (15)	N12A—N13A—N14A	110.58 (14)
C4B—C13B—C12B	120.58 (16)	C11A—N14A—N13A	106.25 (13)
C4B—C13B—H13B	119.7	C11B—N11B—N12B	109.11 (14)
C12B—C13B—H13B	119.7	C11B—N11B—H11B	125.4
C3B—C14B—C12B	120.60 (16)	N12B—N11B—H11B	125.4
C3B—C14B—H14B	119.7	N13B—N12B—N11B	106.27 (14)
C12B—C14B—H14B	119.7	N12B—N13B—N14B	110.78 (14)
N9—C9—C10	110.58 (14)	C11B—N14B—N13B	106.26 (14)
N9—C9—H9A	109.5	C9—N9—H9C	109.5
C10—C9—H9A	109.5	C9—N9—H9D	109.5
N9—C9—H9B	109.5	H9C—N9—H9D	109.5
C10—C9—H9B	109.5	C9—N9—H9E	109.5
H9A—C9—H9B	108.1	H9C—N9—H9E	109.5
N10—C10—C9	110.26 (14)	H9D—N9—H9E	109.5
N10—C10—H10A	109.6	C10—N10—H10C	109.5
C9—C10—H10A	109.6	C10—N10—H10D	109.5
N10—C10—H10B	109.6	H10C—N10—H10D	109.5
C9—C10—H10B	109.6	C10—N10—H10E	109.5
H10A—C10—H10B	108.1	H10C—N10—H10E	109.5
N4A—C1A—N1A	110.91 (14)	H10D—N10—H10E	109.5
N4A—C1A—C2A	124.96 (14)	C1A—N1A—N2A	105.64 (13)
N1A—C1A—C2A	124.13 (14)	N3A—N2A—N1A	108.65 (13)
C3A—C2A—C4A	118.34 (15)	N2A—N3A—N4A	110.11 (13)
C3A—C2A—C1A	121.17 (14)	C1A—N4A—N3A	104.69 (13)
C4A—C2A—C1A	120.49 (15)	C1B—N1B—N2B	105.69 (13)
C14A—C3A—C2A	120.94 (16)	N3B—N2B—N1B	108.54 (13)
C14A—C3A—H3A	119.5	N2B—N3B—N4B	109.96 (13)
C2A—C3A—H3A	119.5	C1B—N4B—N3B	105.03 (13)
C13A—C4A—C2A	120.80 (15)	H1B—O1—H1A	108.9
C13A—C4A—H4A	119.6	H2A—O2—H2B	110.7

D—H···A	D—H	H···A	D···A	D—H···A
O2—H2B···N4Ai	0.82	2.02	2.843 (2)	177.
O2—H2A···N13A	0.85	2.08	2.919 (2)	173.
O1—H1A···N4B	0.84	2.02	2.857 (2)	179.
O1—H1B···N13Bii	0.85	2.10	2.946 (2)	174.
N10—H10E···N3Aiii	0.89	2.02	2.869 (2)	160.
N10—H10D···N1Biv	0.89	2.00	2.848 (2)	159.
N10—H10C···N14Av	0.89	2.08	2.938 (2)	163.
N9—H9E···N1Avi	0.89	1.98	2.8517 (19)	165.
N9—H9D···N14Bii	0.89	2.13	2.888 (2)	143.
N9—H9C···N3B	0.89	2.01	2.856 (2)	159.
N11B—H11B···O2	0.86	1.86	2.685 (2)	161.
N11A—H11A···O1	0.86	1.87	2.6903 (19)	160.

Table 1

Hydrogen-bond geometry (Å, °)

D—H⋯A	D—H	H⋯A	D⋯A	D—H⋯A
O2—H2B⋯N4Ai	0.82	2.02	2.843 (2)	177
O2—H2A⋯N13A	0.85	2.08	2.919 (2)	173
O1—H1A⋯N4B	0.84	2.02	2.857 (2)	179
O1—H1B⋯N13Bii	0.85	2.10	2.946 (2)	174
N10—H10E⋯N3Aiii	0.89	2.02	2.869 (2)	160
N10—H10D⋯N1Biv	0.89	2.00	2.848 (2)	159
N10—H10C⋯N14Av	0.89	2.08	2.938 (2)	163
N9—H9E⋯N1Avi	0.89	1.98	2.8517 (19)	165
N9—H9D⋯N14Bii	0.89	2.13	2.888 (2)	143
N9—H9C⋯N3B	0.89	2.01	2.856 (2)	159
N11B—H11B⋯O2	0.86	1.86	2.685 (2)	161
N11A—H11A⋯O1	0.86	1.87	2.6903 (19)	160

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