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

Sr[Mo₂O₂F₉]₂·HF and Ba[Mo₂O₂F₉]₂·2HF, which contain HF molecules of crystallization are synthesized and characterized. An explanation for the conditions leading to the formation of mono- or dinuclear oxyfluoridomolybdate anions is given. The Mo(V) compound Ba[MoOF₅] is synthesized directly for the first time by reacting BaCl₂ with MoCl₅ under hydrofluorothermal conditions and its crystal structure model improved.

The reactions of SrF₂ and BaF₂ with MoOF₄ in aHF at 80 °C are shown to yield the Mo(VI) compounds Sr[Mo₂O₂F₉]₂·HF and Ba[Mo₂O₂F₉]₂·2HF. The stoichiometric ratio of metal fluoride and MoOF₄ determines the formation of mono- or dinuclear oxyfluoridomolybdate anions. The Mo(V) compound Ba[MoOF₅] is synthesized directly for the first time to check its previously reported crystal structure by reacting BaCl₂ with MoCl₅ 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.

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