Effect of the Solvent on the Crystallographic and Magnetic Properties of rhenium(IV) Complexes Based on 2,2′-Bipyrimidine Ligand

Abstract

Two solvated rhenium(IV) complexes with formula [ReCl4(bpym)]·MeCN (1) and [ReCl4(bpym)]·CH3COOH·H2O (2) [bpym = 2,2'-bipyrimidine] have been prepared and characterized by means of Fourier transform infrared spectroscopy (FT–IR), scanning electron microscopy and energy dispersive X-ray analysis (SEM–EDX), single-crystal X-ray diffraction (XRD) and SQUID magnetometer. 1 and 2 crystallize in the monoclinic system with space groups P21/n and P21/c, respectively. In both compounds, the Re(IV) ion is six-coordinate and bound to four chloride ions and two nitrogen atoms of a 2,2’-bipyrimidine molecule forming a distorted octahedral geometry around the metal ion. In the crystal packing of 1 and 2, intermolecular halogen⋯halogen and π⋯halogen type interactions are present. Hydrogen bonds take place only in the crystal structure of 2. Both compounds exhibit an akin crystal framework based on halogen bonds. Variable-temperature dc magnetic susceptibility measurements performed on microcrystalline samples of 1 and 2 show a similar magnetic behavior for both compounds, with antiferromagnetic exchange between the Re(IV) ions connected mainly through intermolecular Re-Cl···Cl-Re interactions.