Ethane-1,2-diaminium bis­{5-[4-(1H-tetra­zol-5-yl)phen­yl]tetra­zolide} dihydrate

Chun-Rong Li; Zheng-Qiang Xia

doi:10.1107/S1600536811034143

. 2011 Aug 27;67(Pt 9):o2481. doi: 10.1107/S1600536811034143

Ethane-1,2-diaminium bis{5-[4-(1H-tetrazol-5-yl)phenyl]tetrazolide} dihydrate

Chun-Rong Li ^a, Zheng-Qiang Xia ^b,^*

PMCID: PMC3200657 PMID: 22059036

Abstract

In the two anions of the title salt, C₂H₁₀N₂ ²⁺·2C₈H₅N₈ ⁻·2H₂O, the central aromatic rings make dihedral angles of 13.53 (6) and 6.53 (7)° with the deprotonated tetrazole rings, and 11.39 (6) and 10.41 (9)° with the other tetrazole groups. In the crystal, the cations, anions and water molecules 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 interactions between benzene rings [intercentroid distances are 3.8482 (4) and 3.9621 (5) Å] and between tetrazole rings [intercentroid 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 _r = 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
Δρ_max = 0.19 e Å⁻³
Δρ_min = −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.

Supplementary Material

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

e-67-o2481-sup1.cif^{(21.6KB, cif)}

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

e-67-o2481-Isup2.hkl^{(200.4KB, hkl)}

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

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

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⋯N1B^iv	0.89	2.00	2.848 (2)	159
N10—H10C⋯N14A^v	0.89	2.08	2.938 (2)	163
N9—H9E⋯N1A^vi	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

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

Acknowledgments

We gratefully acknowledge the National Science Foundation of China (grant No. 20873100) and Natural Science Foundation of Shaanxi Province (grant No. FF10091).

supplementary crystallographic information

Comment

Recently, 5,5'-(1,4-phenylene)-bis(1H-tetrazole) has been widely employed in the construction of many useful metal-organic frameworks (Liu et al., 2010; Ouellette et al., 2009; Dinca et al., 2006). This compound attracted our attention and our recent investigation on it (Qiao et al., 2011) has revealed its potential applications in energetic materials as the additives for the propellant. However, reports on its use in the construction of co-crystals are very scarce. Here, in the reaction of ethylenediamine, 5,5'-(1,4-phenylene)bis(1H-tetrazole) and PbCl₂ under hydrothermal conditions, we have unexpectedly obtained the title compound, C₂H₁₀N₂²⁺.2C₈H₅N₈^-.2H₂O, and determined its crystal structure.

The asymmetric unit of the title salt is composed of one ethylenediaminium cation, two 5-[4-(1H-tetrazol-5-yl)phenyl]tetrazolide monoanions and two water molecules (Fig.1). Both the amine N atoms of the ethylenediaminium cation are protonated. The geometric parameters are within the normal ranges.

In the crystal structure, the two terminal tetrazole rings of the anions are nearly coplanar with the dihedral angles of 5.03 (7) or 6.37 (10)°. It is noteworthy that there are two types of π-π stacking interactions: one occurs between benzene rings with centroid-centroid distances of 3.8482 (4) and 3.9621 (5) Å, the other occurs between tetrazole rings with centroid-centroid distances of 3.4350 (4) and 3.7169 (4) Å. Thus, a wide range of hydrogen bonds (O—H···N, N—H···O and N—H···N) (Table 1) and π-π stacking interactions contribute to the formation of the supramolecular network (Fig. 2).

Experimental

Lead chloride (0.0278 g, 0.1 mmol) and 5,5'-(1,4-phenylene)-bis(1H-tetrazole) (0.0215 g, 0.1 mmol) were added to water (6 ml). The pH of this solution was adjusted to neutral with ethylenediamine solution. The solution was sealed in a 10-ml Teflon-lined stainless reactor at 393 K for 3 days. After the sample was cooled to room temperature at a rate of 5 K/h, the colorless block crystals suitable for X-ray analysis were obtained.