Compounds containing the dioxychloronium cation, [ClO2]+, were obtained from reactions of ClF3 with various oxides such as TiO2, MoO3, Re2O7, SnO, P2O5, As2O5, and Nb metal, as the latter contained oxide as an impurity. Partial hydrolysis of [ClF2][IrF6] led to the formation of [ClO2][IrF6]. The crystal structures of the compounds were determined by single‐crystal X‐ray diffraction, which showed that depending on the starting material [ClO2]+ salts with the fluoridometallate anions [TiF3/2F3/1]2]−, [Nb3F16]−, [IrF6]−, [SnF2/2F4/1]− [PF6]−, and [AsF6]−, or with the oxidofluoridometallate anions [Mo3O3F13]− and [Re3O6F10]−, were obtained. Bent [ClO2]+ cations with short Cl ⋅ ⋅ ⋅ μ−F contacts of surrounding F atoms of the anions with the Cl atom are present in the crystal structures, leading to coordination numbers of 2+4 or 2+6 for the Cl atom. Various structural motifs are observed, which range from molecular, columnar, ladder‐like, to layer and framework structures. The salts were furthermore characterized by Raman spectroscopy and solid‐state quantum‐chemical calculations. Covalent Cl−O bonds and ionic Cl ⋅ ⋅ ⋅ μ−F interactions are indicated by the calculations. [ABSTRACT FROM AUTHOR]
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