Na2FeO3 is Caswellsilverite-like structured and crystallizes in the hexagonal P6_3/mcm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to six equivalent O(1) atoms. In the second Na site, Na(2) is bonded to six equivalent O(1) atoms to form NaO6 octahedra that share edges with six equivalent Fe(1)O6 octahedra. Fe(1) is bonded to six equivalent O(1) atoms to form FeO6 octahedra that share edges with three equivalent Na(2)O6 octahedra and edges with three equivalent Fe(1)O6 octahedra. O(1) is bonded to one Na(2), three equivalent Na(1), and two equivalent Fe(1) atoms to form a mixture of distorted corner, edge, and face-sharing ONa4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 0-48°.
Na2FeO3 is Caswellsilverite-like structured and crystallizes in the hexagonal P6_3/mcm space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded in a 6-coordinate geometry to six equivalent O(1) atoms. There are two shorter (2.24 Å) and four longer (2.42 Å) Na(1)-O(1) bond lengths. In the second Na site, Na(2) is bonded to six equivalent O(1) atoms to form NaO6 octahedra that share edges with six equivalent Fe(1)O6 octahedra. All Na(2)-O(1) bond lengths are 2.21 Å. Fe(1) is bonded to six equivalent O(1) atoms to form FeO6 octahedra that share edges with three equivalent Na(2)O6 octahedra and edges with three equivalent Fe(1)O6 octahedra. All Fe(1)-O(1) bond lengths are 1.92 Å. O(1) is bonded to one Na(2), three equivalent Na(1), and two equivalent Fe(1) atoms to form a mixture of distorted corner, edge, and face-sharing ONa4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 0-48°.