The chemistry of hypercoordination has been a subject of fundamental interest, especially for understanding structures that challenge conventional wisdom. The small ionic radii of Fe ions typically result in coordination numbers of 4 or 6 in stable Fe-bearing ionic compounds. While 8-coordinated Fe has been observed in highly compressed oxides, the pursuit of hypercoordinated Fe still faces significant challenges due to the complexity of synthesizing the anticipated compound with another suitable anion. Through firstprinciples simulation and advanced crystal structure prediction methods, we predict that an orthorhombic phase of FeF3 with exclusively 8-coordinated Fe is energetically stable above 18 GPa—a pressure more feasibly achieved compared to oxides. Inspired by this theoretical result, we conducted extensive experiments using a laser-heated diamond anvil cell technique to investigate the crystal structures of FeF3 at high-pressure conditions. We successfully synthesized the predicted orthorhombic phase of FeF3 at 46 GPa, as confirmed by in situ experimental X-ray diffraction data. This work establishes a new ionic compound featuring rare 8- coordinated Fe in a simple binary Fe-bearing system and paves the way for discovering Fe hypercoordination in similar systems.

Structure prediction,High pressure synthesis,Hypercoordination,Eight-Coordinated ir