Crystal Structures of Photochemically Prepared (Xe2F11)2(MF6) (M = Sn, Pb) and (XeF5)4(Sn5F24) Containing Six‐ and Seven‐Coordinated Tin(IV)

Abstract

Single crystals of [Xe2F11]2[SnF6], [Xe2F11]2[PbF6], and [XeF5]4[Sn5F24] were grown from saturated aHF solutions upon crystallizations. The crystal structures of isotypic [Xe2F11]2[SnF6] and [Xe2F11]2[PbF6] consist of [Xe2F11]+ cations and [MF6]2– anions (M = Sn, Pb) that interact by means of fluorine bridge contacts. The single crystal structure determination of [XeF5]4[Sn5F24] reveals that it is built of two‐dimensional ([Sn5F24]4–)∞ grids and [XeF5]+ cations located between them. The 2D grids have a wave‐like conformation. The ([Sn5F24]4–)∞ layer contains, both, six‐ and seven‐coordinated Sn(IV) interconnected by bridging fluorine atoms. The coordination of Sn(IV) by seven fluorine atoms is unprecedented. Attempts to synthesize and grow single crystals of the [XeF5][MF5] (M = Zr, Hf, Ni, Pd) compounds failed.