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This paper reports the crystal structure of tetra­sodium diiron tris(phosphate), Na 4 Fe 2+ Fe 3+ (PO 4 ) 3 , which has been synthesized hydro­thermally at 773 K and 0.1 GPa. The crystal structure has been refined in the space group  Rc  and is identical to that of γ-NASICON. The heteropolyhedral framework is based on a regular alternation, in three dimensions, of corner-sharing PO 4  tetra­hedra and FeO 6  octa­hedra, constituting so-called ‘lantern units’ stacked along the  c  axis. The Na +  cations are distributed over two crystallographic sites: the six-coordinated Na1 site which lies between two ‘lantern units’, and the eight-coordinated Na2 site which lies at the same  z  value as the P site.

Na4Fe2+Fe3+(PO4)3, a new synthetic NASICON-type phosphate

Na₄Fe²⁺Fe³⁺(PO₄)₃, a new synthetic NASICON-type phosphate