| Summary: | Two solvated rhenium(IV) complexes with formula [ReCl<sub>4</sub>(bpym)]·MeCN (<b>1</b>) and [ReCl<sub>4</sub>(bpym)]·CH<sub>3</sub>COOH·H<sub>2</sub>O (<b>2</b>) (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. <b>1</b> and <b>2</b> crystallize in the monoclinic system with space groups <i>P</i>2<sub>1</sub>/<i>n</i> and <i>P</i>2<sub>1</sub>/<i>c</i>, 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 <b>1</b> and <b>2</b>, intermolecular halogen⋯halogen and π⋯halogen-type interactions are present. Hydrogen bonds take place only in the crystal structure of <b>2</b>. Both compounds exhibit a similar crystal framework based on halogen bonds. Variable temperature dc magnetic susceptibility measurements performed on microcrystalline samples of <b>1</b> and <b>2</b> 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.
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