Three-Dimensional Network Polymeric Structure of (2-Amino-5 Ammoniopyridinium)[CuCl4]: Crystal Supramolecularity and Magnetic Properties

A single crystal structure determination of the complex (C5H9N3)CuCl4 [henceforth I] has been carried out. It crystallizes in the orthorhombic space group Cmca, with the cell parameters a=6.7053(5) A, b=22.4171(19) A, c=13.4173(9) A, V=2016.8(3) A3, and Z=8. In the complex, the anion is comprised of infinite zigzag chains of monochloro-bridged \(\mathrm{CuCl}_{4}^{2-}\) units ⋯–CuCl3–μ–Cl–CuCl3–μ–Cl–CuCl3–⋯ surrounded by the pyridinium-ammonium cations. The Cu ions are five-coordinate to chloride ions in a distorted square-pyramidal geometry with the zigzag chains formed by corner-sharing polyhedra. The Cu ion is located 0.151 A above the basal plane. In the crystal, there are four intermolecular hydrogen bonding interactions, linking the CuCl chains to the cations to form a 2D-network. The resulting 2D-networks are further linked by aryl⋯aryl (π⋯π) interactions within the cationic chains leading to a 3D-network. Variable temperature magnetic susceptibility data were fit to a one-dimensional S=1/2 antiferromagnetic chain model yielding C=0.44(1) emu-K/mol-Oe and J=−37(1) K.