2-Amino-5-(1H-tetra­zol-5-yl)pyridin-1-ium nitrate

Jing Dai; Xiao-Chun Wen

doi:10.1107/S1600536808030791

. 2008 Sep 27;64(Pt 10):o2028. doi: 10.1107/S1600536808030791

2-Amino-5-(1H-tetrazol-5-yl)pyridin-1-ium nitrate

Jing Dai ^a, Xiao-Chun Wen ^a,^*

PMCID: PMC2959428 PMID: 21201222

Abstract

In the cation of the title compound, C₆H₇N₆ ⁺·NO₃ ⁻, the pyridine and tetrazole rings are essentially coplanar, exhibiting a dihedral angle of 6.30 (6)°. In the crystal structure, N—H⋯O, N—H⋯N, C—H⋯O and C—H⋯N hydrogen bonds form a three-dimensional network.

Related literature

For general background on the chemistry of tetrazole derivatives, see: Dunica et al. (1991 ▶); Wittenberger & Donner (1993 ▶); Zou et al. (2007 ▶); Xiong et al. (2002 ▶). For the crystal structures of related compounds, see: Dai & Fu (2008 ▶); Wang et al. (2005 ▶).

Experimental

Crystal data

C₆H₇N₆ ⁺·NO₃ ⁻
M _r = 225.19
Monoclinic,
a = 8.3797 (17) Å
b = 6.9314 (14) Å
c = 15.881 (3) Å
β = 94.31 (3)°
V = 919.8 (3) Å³
Z = 4
Mo Kα radiation
μ = 0.13 mm⁻¹
T = 298 (2) K
0.30 × 0.22 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.916, T _max = 0.970
8766 measured reflections
2023 independent reflections
1520 reflections with I > 2σ(I)
R _int = 0.041

Refinement

R[F ² > 2σ(F ²)] = 0.049
wR(F ²) = 0.120
S = 1.07
2023 reflections
173 parameters
All H-atom parameters refined
Δρ_max = 0.15 e Å⁻³
Δρ_min = −0.18 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/PC (Sheldrick, 2008 ▶); software used to prepare material for publication: SHELXTL/PC.

Supplementary Material

Crystal structure: contains datablocks I, global. DOI: 10.1107/S1600536808030791/rz2247sup1.cif

e-64-o2028-sup1.cif^{(15.8KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808030791/rz2247Isup2.hkl

e-64-o2028-Isup2.hkl^{(99.5KB, 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⋯O2ⁱ	0.95 (2)	2.55 (2)	3.328 (2)	138.7 (18)
N1—H1A⋯O3ⁱ	0.95 (2)	1.84 (3)	2.764 (2)	163 (2)
N5—H5⋯O1ⁱⁱ	0.91 (2)	2.11 (2)	2.989 (2)	163 (2)
N5—H5⋯O3ⁱⁱ	0.91 (2)	2.21 (2)	2.908 (2)	133.3 (19)
N6—H6A⋯O1ⁱⁱⁱ	0.88 (3)	2.31 (3)	3.074 (3)	145 (2)
N6—H6B⋯O2ⁱⁱⁱ	0.90 (3)	2.48 (3)	2.908 (2)	110 (2)
N6—H6B⋯N2^iv	0.90 (3)	2.32 (3)	3.176 (3)	158 (3)
C1—H1⋯O3ⁱⁱ	0.96 (2)	2.60 (2)	3.124 (2)	114.4 (16)
C1—H1⋯O2ⁱ	0.96 (2)	2.38 (2)	3.308 (2)	161.5 (18)
C3—H3⋯N4^v	0.95 (2)	2.55 (2)	3.305 (3)	136.3 (16)

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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 to Professor R.-G. Xiong.

supplementary crystallographic information

Comment

The tetrazole functional group has found a wide range of applications in coordination chemistry as ligand, in medicinal chemistry as a metabolically stable surrogate for the carboxylic acid group, and in materials science as high density energy material (Wang et al., 2005; Xiong et al., 2002; Zou et al., 2007; Dunica et al., 1991; Wittenberger & Donner, 1993). We report here the crystal structure of the title compound, 5-(1H-tetrazol-5-yl)pyridin-2-amine-1-ium nitrate.

In the cation of the title compound (Fig. 1) the pyridine and tetrazole rings are essentially coplanar with a dihedral angle of only 6.30 (6)°. Bond distances and angles of the tetrazole ring are within the usual range (Wang et al., 2005; Dai & Fu, 2008). The pyridine N atom is protonated. The crystal packing is consolidated by N—H···O, N—H···N, C—H···O and C—H···N hydrogen bonds to form a three-dimentional network. (Table 1, Fig. 2).

Experimental

2-Amino-5-cyanopyridine (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 nitrate acid (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/nitric acid (50:1 v/v) solution.