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.