Syntheses and structural trends of the InxMo15S19 (0 <= x <= 3.7) compounds containing Mo-6 and Mo-9 clusters

摘要

The InxMo15S19 (x = 0.0, 0.10, 0.20, 0.36, 0.50, 0.70, 1.2 and 2.9) compounds were obtained from oxidation of the solid-state compound In3.7Mo15S19 by iodine in sealed glass tube at temperatures below 300degreesC. Their crystal structures were solved and refined from X-ray single crystal data in the hexagonal space group P6(3)/m. The Mo-S framework of the InxMo15S19 compounds consists of an equal mixture of Mo6S8S6 and Mo9S11S6 Cluster units interconnected through Mo-S bonds. The X-ray single-crystal study of the InxMo15S19 (0 less than or equal to x less than or equal to 3.7) compounds has allowed us to follow the evolution of the Mo-Mo distances within the Mo-6 and Mo-9 clusters as a function of the cationic charge. Quantum chemical calculations carried out in order to understand these trends as well as magnetic susceptibility measurements are also reported. (C) 2004 Elsevier Inc. All rights reserved.