3-(1H-Tetra­zol-5-yl)pyridinium chloride

Jing Dai; Miao-Jia Yu

doi:10.1107/S1600536809018972

. 2009 May 23;65(Pt 6):o1391. doi: 10.1107/S1600536809018972

3-(1H-Tetrazol-5-yl)pyridinium chloride

Jing Dai ^a,^*, Miao-Jia Yu ^a

PMCID: PMC2969833 PMID: 21583237

Abstract

In the cation of the title compound, C₆H₆N₅ ⁺·Cl⁻, the pyridinium and tetrazole rings are nearly coplanar, making a dihedral angle of 5.05 (12)°. The cations and anions are connected by intermolecular N—H⋯Cl hydrogen bonds, forming a centrosymmetric [2 + 2] aggregate. The aggregates are stacked along the a axis.

Related literature

For applications of tetrazole derivatives in coordination chemistry, see: Xiong et al. (2002 ▶); Wang et al. (2005 ▶). For the crystal structures of related compounds, see: Dai & Fu (2008 ▶); Wen (2008 ▶).

Experimental

Crystal data

C₆H₆N₅ ⁺·Cl⁻
M _r = 183.61
Monoclinic,
a = 4.2741 (9) Å
b = 8.1992 (16) Å
c = 23.559 (5) Å
β = 94.72 (3)°
V = 822.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 298 K
0.30 × 0.25 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.883, T _max = 0.921
8164 measured reflections
1862 independent reflections
1431 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.040
wR(F ²) = 0.104
S = 1.03
1862 reflections
109 parameters
H-atom parameters constrained
Δρ_max = 0.22 e Å⁻³
Δρ_min = −0.28 e Å⁻³

Data collection: CrystalClear (Rigaku, 2005 ▶); cell refinement: CrystalClear; data reduction: CrystalClear; program(s) used to solve structure: SHELXS97 (Sheldrick, 2008 ▶); program(s) used to refine structure: SHELXL97 (Sheldrick, 2008 ▶); molecular graphics: SHELXTL (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536809018972/is2410sup1.cif

e-65-o1391-sup1.cif^{(13.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536809018972/is2410Isup2.hkl

e-65-o1391-Isup2.hkl^{(91.7KB, 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⋯Cl1ⁱ	0.86	2.25	3.0625 (18)	157
N2—H2⋯Cl1ⁱⁱ	0.86	2.23	3.0790 (18)	171

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Symmetry codes: (i) Inline graphic ; (ii) .

Acknowledgments

This work was supported by a start-up grant from Southeast University to Professor Ren-Gen Xiong.

supplementary crystallographic information

Comment

In the past few years, more and more people have focused on the chemistry of tetrazole derivatives because of their multiple coordination modes as ligands to metal ions and for the construction of novel metal-organic frameworks (Wang et al., 2005; Xiong et al., 2002; Wen, 2008). We report here the crystal structure of the title compound, 3-(1H-tetrazol-5-yl)pyridinium chloride.

In the title compound, the pyridine N atom is protonated (Fig.1). The pyridinium and the tetrazole rings are nearly coplanar and only twisted from each other by a dihedral angle of 5.05 (12) °. The geometric parameters of the tetrazole rings are comparable to those in related molecules (Wang et al., 2005; Dai & Fu, 2008).

The crystal packing is stabilized by aromatic π–π interactions between the benzene rings of the neighbouring cation systems. The Cg···Cgⁱⁱⁱ distance is 4.274 (2) Å; Cg is the centroide of the C1—C6 benzene ring [symmetry code: (iii) x - 1, y, z]. The molecular packing is further stabilized by intermolecular N—H···Cl hydrogen bonds (Fig. 2 and Table 1).

Experimental

Picolinonitrile (30 mmol), NaN₃ (45 mmol), NH₄Cl (33 mmol) and DMF (50 ml) were added in a flask under nitrogen atmosphere and the mixture stirred at 110°C for 20 h. The resulting solution was then poured into ice-water (100 ml), and a white solid was obtained after adding HCl (6 M) till pH=6. The precipitate was filtered and washed with distilled water. Colourless block-shaped crystals suitable for X-ray analysis were obtained from the crude product by slow evaporation of an ethanol/HCl (50:1 v/v) solution.