2-Amino-5-(1H-tetra­zol-5-yl)pyridinium chloride

Jing Dai; Xiao-Chun Wen

doi:10.1107/S1600536808031164

. 2008 Oct 31;64(Pt 11):o2232. doi: 10.1107/S1600536808031164

2-Amino-5-(1H-tetrazol-5-yl)pyridinium chloride

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

PMCID: PMC2959660 PMID: 21581086

Abstract

In the title salt, C₆H₇N₆ ⁺·Cl⁻, there are two organic cations with similar conformations and two chloride anions in the asymmetric unit. The pyridine and tetrazole rings are essentially coplanar in each cation, with dihedral angles of 4.94 (15) and 5.41 (14)°. The pyridine N atoms are protonated. The crystal packing is stabilized by N—H⋯N and N—H⋯Cl hydrogen bonds, forming an infinite sheets parallel to the (101).

Related literature

For uses of tetrazole derivatives, see: Dai & Fu (2008 ▶); Wang et al. (2005 ▶); Wen (2008 ▶); Xiong et al. (2002 ▶).

Experimental

Crystal data

C₆H₇N₆ ⁺·Cl⁻
M _r = 198.63
Monoclinic,
a = 14.043 (3) Å
b = 13.238 (3) Å
c = 9.5766 (19) Å
β = 109.35 (3)°
V = 1679.7 (6) Å³
Z = 8
Mo Kα radiation
μ = 0.41 mm⁻¹
T = 298 (2) K
0.45 × 0.25 × 0.20 mm

Data collection

Rigaku Mercury2 diffractometer
Absorption correction: multi-scan (CrystalClear; Rigaku, 2005 ▶) T _min = 0.859, T _max = 0.920
16820 measured reflections
3855 independent reflections
3123 reflections with I > 2σ(I)
R _int = 0.034

Refinement

R[F ² > 2σ(F ²)] = 0.048
wR(F ²) = 0.125
S = 1.11
3855 reflections
235 parameters
H-atom parameters constrained
Δρ_max = 0.28 e Å⁻³
Δρ_min = −0.23 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/S1600536808031164/bh2196sup1.cif

e-64-o2232-sup1.cif^{(18.2KB, cif)}

Structure factors: contains datablocks I. DOI: 10.1107/S1600536808031164/bh2196Isup2.hkl

e-64-o2232-Isup2.hkl^{(189KB, 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—H1⋯N5ⁱ	0.86	2.59	3.317 (2)	143
N1—H1⋯N6ⁱ	0.86	2.04	2.894 (2)	171
N2—H2A⋯N5ⁱ	0.86	2.15	2.972 (3)	160
N7—H7⋯N11ⁱⁱ	0.86	2.57	3.304 (2)	144
N7—H7⋯N12ⁱⁱ	0.86	2.06	2.913 (2)	169
N8—H8A⋯N11ⁱⁱ	0.86	2.20	3.024 (3)	160
N2—H2B⋯Cl1ⁱⁱⁱ	0.86	2.36	3.2187 (18)	177
N3—H3A⋯Cl2ⁱ	0.86	2.17	3.0047 (19)	165
N8—H8B⋯Cl2^iv	0.86	2.39	3.2432 (18)	172
N9—H9A⋯Cl1^v	0.86	2.18	3.0031 (18)	160

Open in a new tab

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

Acknowledgments

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

supplementary crystallographic information

Comment

Tetrazole derivatives have found a wide range of applications in coordination chemistry 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; Dai & Fu, 2008). We report here the crystal structure of the title salt (Fig. 1).

The title compound contains two organic cations with similar conformation and two Cl^- ions in the asymmetric unit. The pyridine N atoms are protonated. The pyridine rings and tetrazole rings are nearly coplanar and are twisted from each other by a dihedral angle of only 4.94 (15) and 5.41 (14)°. The packing of ions is stabilized by N—H···N and N—H···Cl hydrogen bonds, to form an infinite two-dimensional layers parallel to the (1 0 1) plane in the crystal (Table 1 and Fig. 2).

Experimental

2-Amino-5-cyanopyridine (30 mmol), NaN ₃ (45 mmol), NH₄Cl (33 mmol) and DMF (50 ml) were mixed in a flask under nitrogen atmosphere, and the mixture stirred at 383 K for 20 h. The resulting solution was then poured into ice-water (100 ml), and a white solid was obtained after adding hydrochloric acid (6 M) until 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/hydrochloric acid (50:1 v/v) solution.