Hydrothermal synthesis and characterization of a new inorganic–organic hybrid compound AMP[ZnCl 3] (AMP = 2-aminomethylpyridinium)

Abstract

A novel organic–inorganic hybrid complex [(2-NH 2CH 2C 5H 4N)ZnCl 3] has been hydrothermally synthesized and characterized by single crystal X-ray diffraction, thermal analysis and spectroscopic studies. The compound crystallizes in the triclinic system, space group P 1 ¯ , a = 7.5339(9), b = 7.589(2), c = 9.365(2) Å, α = 104.55(2)°, β = 97.22(1)°, γ = 87.88(2)°, V = 513.6(2), Z = 2. In the title compound the 2-aminomethylpyridine acts as a ligand covalently linked to Zn(II) cation to form a slightly distorted ZnCl 3N tetrahedral environment. Each [Zn(C 6H 8N 2)Cl 3] unit is connected to one neighbor by a pair of hydrogen bonds between the apical chlorides and amine hydrogen atoms and to the other by a couple of π–π stacking interactions between the aromatic rings of the coordinated ligands forming a novel one-dimensional chain-like arrangement. The title complex is the first one that contains both coordinated and hydrogen bonded 2-aminomethylpyridine. Solid state 13C and 15N CP-MAS-NMR spectroscopies are in agreement with the X-ray structure. Ab initio calculations allow the attribution of carbons and nitrogen to the independent crystallographic sites. The Raman spectroscopy confirmed the presence of Zn–Cl and Zn–N bonds.