Synthesis and Structure of Two Ionic Copper Indium Selenolate Cluster Complexes [As(C 6 H 5 ) 4 ] 2 [Cu 6 In 4 (SeC 6 H 5 ) 16 Cl 4 ] and [As(C 6 H 5 ) 4 ][Cu 7 In 4 (SeC 6 H 5 ) 20 ]

The reaction of PhSeSiMe 3 , CuCl, InCl 3 , and Ph 4 AsCl in CH 2 Cl 2 results in crystals of the structurally closely related, ionic clusters (AsPh 4 ) 2 [Cu 6 In 4 Cl 4 (SePh) 16 ] and (AsPh 4 )[Cu 7 In 4 (SePh) 20 ], with product ratios dependent on the initial PhSeSiMe 3 concentration. Both molecules display a fused four‐adamantoid structure related to the solid‐state structure of CuInSe 2 . Since the crystallographic analysis for [Cu 7 In 4 (SePh) 20 ] – remained ambiguous with respect to the assignment of one of the copper atoms, we performed a high‐resolution mass spectrometric analysis as well as DFT computations to address this problem. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)