Synthesis and Characterization of Cs2Mo6X14 (X = Br or I) Hexamolybdenum Cluster Halides: Efficient Mo6 Cluster Precursors for Solution Chemistry Syntheses

Cs2Mo6Br14 (1) and Cs2Mo6I14 (2) have been synthesized by solid state chemistry techniques and structurally characterized by single crystal X‐ray diffraction. They crystallize in the P3¯1c space group (Nr. 163) with the following lattice parameters: a = 10.1925(1) Å, c = 15.0690(3) Å, Z = 2 for 1; a = 10.804(5) Å, c = 16.258(5) Å, Z = 2 for 2. These clusters halides, whose structures are related to that of Cs2Mo6Cl8Br6, are built up from discrete [(Mo6Xi8)Xa6]2‐ anionic units (X = Br, I) stacked according to an hexagonal close‐packing arrangement. In the present work, the influence of the halogen on the cesium sites will be evidenced and discussed. Furthermore, a simple high yield preparation method of (TBA)2Mo6Xi8Xa6 will be proposed starting from Cs2Mo6X14.