Hexaaqua­magnesium dibromide 5-(pyridinium-3-yl)tetra­zol-1-ide

Jing Dai; Xin-Yuan Chen

doi:10.1107/S1600536810052992

. 2010 Dec 24;67(Pt 1):m113. doi: 10.1107/S1600536810052992

Hexaaquamagnesium dibromide 5-(pyridinium-3-yl)tetrazol-1-ide

Jing Dai ^a,^*, Xin-Yuan Chen ^a

PMCID: PMC3050346 PMID: 21522526

Abstract

In the title compound, [Mg(H₂O)₆]Br₂·2C₆H₅N₅, the Mg^II atom, lying on an inversion center, is coordinated by six water molecules in a distorted octahedral geometry. The pyridine and tetrazole rings in the 5-(pyridinium-3-yl)tetrazol-1-ide zwitterion are nearly coplanar, twisted from each other by a dihedral angle of 5.70 (1)°. The zwitterions, Br anions and complex cations are connected by O—H⋯Br, O—H⋯N and N—H⋯Br hydrogen bonds, leading to the formation of a three-dimensional network.

Related literature

For tetrazole derivatives, see: Fu et al. (2008 ▶); Zhao et al. (2008 ▶). For the crystal structures and properties of related compounds, see: Fu et al. (2007 ▶, 2009 ▶); Fu & Xiong (2008 ▶).

Experimental

Crystal data

[Mg(H₂O)₆]Br₂·2C₆H₅N₅
M _r = 586.53
Triclinic,
a = 7.3439 (15) Å
b = 8.7786 (18) Å
c = 9.5863 (19) Å
α = 94.04 (3)°
β = 90.94 (3)°
γ = 111.75 (3)°
V = 572.0 (2) Å³
Z = 1
Mo Kα radiation
μ = 3.62 mm⁻¹
T = 298 K
0.40 × 0.05 × 0.05 mm

Data collection

Rigaku SCXmini CCD diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.89, T _max = 0.95
5933 measured reflections
2627 independent reflections
2172 reflections with I > 2σ(I)
R _int = 0.040

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.097
S = 1.09
2627 reflections
142 parameters
H-atom parameters constrained
Δρ_max = 0.32 e Å⁻³
Δρ_min = −0.52 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXTL (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXTL; molecular graphics: SHELXTL and DIAMOND (Brandenburg, 1999 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536810052992/hy2389sup1.cif

e-67-0m113-sup1.cif^{(14.5KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536810052992/hy2389Isup2.hkl

e-67-0m113-Isup2.hkl^{(129KB, hkl)}

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
N1—H1A⋯Br1ⁱ	0.86	2.41	3.240 (3)	161
O1W—H1WA⋯N5	0.81	1.98	2.780 (3)	171
O1W—H1WB⋯Br1ⁱⁱ	0.89	2.66	3.382 (3)	138
O2W—H2WA⋯N4	0.86	1.89	2.738 (3)	167
O2W—H2WB⋯Br1ⁱⁱⁱ	0.76	2.53	3.296 (2)	178
O3W—H3WA⋯Br1^iv	0.91	2.48	3.328 (2)	156
O3W—H3WB⋯N2^v	0.96	1.78	2.730 (3)	174

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

Acknowledgments

This work was supported by a start-up grant from Southeast University.

supplementary crystallographic information

Comment

Tetrazole compounds have attracted more attention as phase transition dielectric materials for its applications in micro-electronics, memory storage. With the purpose of obtaining phase transition crystals of 3-(1H-tetrazol-5-yl)pyridine compounds, its interaction with various metal ions has been studied and a series of new materials have been elaborated with this organic molecule (Fu et al., 2007, 2008; Fu & Xiong 2008; Zhao et al., 2008). In this paper, we describe the crystal structure of the title compound.

The asymmetric unit of the title compound (Fig. 1) is composed of one zwitterionic organic molecule, half [Mg(H₂O)₆]²⁺ cation and one Br anion. In the zwitterionic organic molecule, the pyridine N atom is protonated. The pyridine and tetrazole rings are nearly coplanar and only twisted from each other by a dihedral angle of 5.70 (1)°. The geometric parameters of the tetrazole ring are comparable to those in related molecules (Fu et al., 2009; Zhao et al., 2008).

In the crystal structure, the intermolecular hydrogen bonds are formed by all H atoms of the water molecules and pyridine N atoms with the tetrazole N atoms or Br anions. The complex cations [Mg(H₂O)₆]²⁺ and Br anions are linked in the crystal through O—H···Br hydrogen bonds into an infinite cation–anion sheet parallel to (0 0 1). The two-dimensional sheets are linked by organic molecules through O—H···N and N—H···Br hydrogen bonds into a three-dimensional network (Table 1 and Fig. 2).

Experimental

MgBr₂.6H₂O (2 mmol) and 3-(1H-tetrazol-5-yl)pyridine (0.528 g, 2 mmol) were dissolved in 70% methanol aqueous solution, and then 2 ml HBr was added. Single crystals suitable for X-ray diffraction analysis were obtained by slow evaporation of the solution at room temperature after two weeks. The crystals were colourless, block, and of average size 0.2×0.3×0.4 mm.

The permittivity measurement shows that there is no phase transition within temperature range from 100 to 400 K, and the permittivity is 9.1 at 1 MHz at room temperature.