Synthesis, structure and DFT calculations of the first bioctahedral chalcohalide rhenium cluster complex (Et4N)4(Me2NH2)2[Re12CS17Br6]

The first example of dodecanuclear chalcohalide rhenium cluster complex, (Et4N)4(Me2NH2)2[Re12CS17Br6] (1), has been synthesized by reaction of polymeric cluster solid Re12CS17 with excess of Et4NBr in boiling DMF. The compound was characterized by a set of methods, including IR and UV–Vis spectroscopy, elemental analysis, EDS, mass-spectrometry, single-crystal X-ray diffraction analysis, and quantum-chemical calculations. The crystal structure presents an interesting case of 1D supramolecular architecture based on notably short Br⋯Br interactions of 3.432 A between the terminal bromide trans-ligands of adjacent [Re12CS17Br6]6− cluster anions. The DFT calculations performed for the [Re12CS17Br6]6− anion showed good agreement between calculated and experimental data.