Synthesis and Characterization of Cs 2 Mo 6 X 14 (X = Br or I) Hexamolybdenum Cluster Halides: Efficient Mo 6 Cluster Precursors for Solution Chemistry Syntheses

Cs 2 Mo 6 Br 14 (1) and Cs 2 Mo 6 I 14 (2) have been synthesized by solid state chemistry techniques and structurally characterized by single crystal X‐ray diffraction. They crystallize in the P 3¯1 c 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 Cs 2 Mo 6 Cl 8 Br 6 , are built up from discrete [(Mo 6 X i 8 )X a 6 ] 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) 2 Mo 6 X i 8 X a 6 will be proposed starting from Cs 2 Mo 6 X 14 .