The Heteroleptic Cluster Cation [(W 6 I 8 )I 3 (CH 3 CN) 3 ] +

The iodide‐rich compound [(W 6 I 8 )I 3 (CH 3 CN) 3 ]I 9 was synthesized solvothermally from W 6 I 22 and I 2 in acetonitrile. The refined crystal structure reveals the presence of the novel heteroleptic cluster cation [(W 6 I 8 )I 3 (CH 3 CN) 3 ] + containing the [W 6 I 8 ] 4+ cluster with an octahedral tungsten cluster core, coordinated by three apical iodido and three acetonitrile ligands via cluster vertices. The iodide‐rich starting material W 6 I 22 with the addition of I 2 , produces the heptaiodide ion (I 7 ) – that is present in the structure of [(W 6 I 8 )I 3 (CH 3 CN) 3 ](I 7 ) · I 2 . The novelty of this compound is based on the cationic nature of the [(W 6 I 8 )I 3 (CH 3 CN) 3 ] + cluster after anionic [(W 6 I 8 )I 6 ] 2– clusters and their ligand (L) substituted derivatives [(W 6 I 8 )L 6 ] 2– have been widely reported for their versatile photophysical properties.