Crystal Structures of Xenon(VI) Salts: XeF 5 Ni(AsF 6 ) 3 , XeF 5 AF 6 (A = Nb, Ta, Ru, Rh, Ir, Pt, Au), and XeF 5 A 2 F 11 (A = Nb, Ta).

Experiments on the preparation of the new mixed cations XeF 5 M(AF 6 ) 3 (M = Cu, Ni; A = Cr, Nb, Ta, Ru, Rh, Re, Os, Ir, Pt, Au, As), XeF 5 M(SbF 6 ) 3 (M = Sn, Pb), and XeF 5 M(BF 4 ) x (SbF 6 ) 3-x (x = 1, 2, 3; M = Co, Mn, Ni, Zn) salts were successful only in the preparation of XeF 5 Ni(AsF 6 ) 3 . In other cases, mixtures of different products, mostly XeF 5 AF 6 and XeF 5 A 2 F 11 salts, were obtained. The crystal structures of XeF 5 Ni(AsF 6 ) 3 , XeF 5 TaF 6 , XeF 5 RhF 6 , XeF 5 IrF 6 , XeF 5 Nb 2 F 11 , XeF 5 Ta 2 F 11 , and [Ni(XeF 2 ) 2 ](IrF 6 ) 2 were determined for the first time on single crystals at 150 K by X-ray diffraction. The crystal structures of XeF 5 NbF 6 , XeF 5 PtF 6 , XeF 5 RuF 6 , XeF 5 AuF 6 , and (Xe 2 F 11 ) 2 (NiF 6 ) were redetermined by the same method at 150 K. The crystal structure of XeF 5 RhF 6 represents a new structural type in the family of XeF 5 AF 6 salts, which crystallize in four different structural types. The XeF 5 A 2 F 11 salts (M = Nb, Ta) are not isotypic and both represent a new structure type. They consist of [XeF 5 ] + cations and dimeric [A 2 F 11 ] - anions. The crystal structure of [Ni(XeF 2 ) 2 ](IrF 6 ) 2 is a first example of a coordination compound in which XeF 2 is coordinated to the Ni 2+ cation.