The first anhydrous metal fluorosulfate Na3Fe(SO4)2F2 with layered structure prepared via the interesting “tailor” role of fluorine ions based on Na3Fe(SO4)2

• Synthesis of the first anhydrous metal fluorosulfate with layered structure.
• The interesting “tailor” role of fluorine ions has been observed.
• An antiferromagnetic interactions between Fe3+ centers is discovered.

A ferric(III) fluorosulfate Na3Fe(SO4)2F2 has been synthesized under hydrothermal conditions and characterized by X-ray powder diffraction (Pnca, a = 6.6419 Å, b = 8.8115 Å, c = 14.0023 Å). Its crystal structure is constructed by corner-sharing FeO4F2 octahedra and SO4 tetrahedra, which shows a layered character with numerous four- and eight-membered polyhedral rings. These rings further connect and intersect with each other to form the three-dimensional layers. Sodium ions are located at the interspace of these layers and keep the charge balance. This is the first time to note the participation of fluorine atoms in the formation of two-dimensional structure of anhydrous transition metal fluorosulfates. Meanwhile, an interesting “tailor” role of the fluorine ions has also been investigated by comparing the structures of Na3Fe(SO4)2F2 and Na3Fe(SO4)2, indicating the feasibility of fabricating compounds from some known structures with the assistance of halogen ions.

As the first example of anhydrous transitional metal fluorosulfates with layered structure, Na3Fe(SO4)2F2 has been synthesized under hydrothermal conditions.Figure optionsDownload as PowerPoint slide