Syntheses and Crystal Structures of the Novel Salts Sr[MoVI₂O₂F₉]₂·HF, Ba[MoVI₂O₂F₉]₂·2HF, and of Ba[MoVOF₅]

The reactions of SrF 2 and BaF 2 with MoOF 4 in aHF at 80 °C are shown to yield the Mo(VI) compounds Sr[Mo 2 O 2 F 9 ] 2 ·HF and Ba[Mo 2 O 2 F 9 ] 2 ·2HF. The stoichiometric ratio of metal fluoride and MoOF 4 determines the formation of mono‐ or dinuclear oxyfluoridomolybdate anions. The Mo(V) compound Ba[MoOF 5 ] is synthesized directly for the first time to check its previously reported crystal structure by reacting BaCl 2 with MoCl 5 under hydrofluorothermal conditions. All compounds are characterized by single crystal and powder X‐ray diffraction and quantum‐chemical calculations on the solids allow the assignment of the infrared and Raman bands.