Abstract
The Mo 4 tetrahedral metal clusters observed in the crystal structure of GaMo 4S 8-type compounds are described as arising from the deformation of a highly symmetrical structure with MoS 6 octahedral local stoichiometry. Then Mo 4 clusters occur at the crossing of MoS 4 distorted linear chains made of MoS 6 octahedra sharing their opposite edges. The main factors (orbital interactions and electron counts) governing the pairing distortions, which lead to a metal—metal alternation phenomenon and then to cluster formation, are analysed through extended Hückel molecular orbital calculations. It is shown that the tetrahedral clustering corresponds to a multidirectional Peierls distortion in an extended network.
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