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) , b=22.4171(19) , c=13.4173(9) , V=2016.8(3) (3), and Z=8. In the complex, the anion is comprised of infinite zigzag chains of monochloro-bridged units a <-aEuro"CuCl3-mu-Cl-CuCl3-mu-Cl-CuCl3-a <- 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 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 aryla <-aryl (pi a <-pi) 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.