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 center dot center dot center dot Br interactions of 3.432 angstrom 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. (C) 2013 Elsevier Ltd. All rights reserved.