Na2FeO3 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with five equivalent Na(2)O6 octahedra, and edges with five equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-18°. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Fe(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, edges with four equivalent Fe(1)O6 octahedra, and edges with five equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-17°. Fe(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted FeO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with three equivalent Fe(1)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with five equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-16°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent Fe(1) atoms to form a mixture of distorted edge and corner-sharing ONa4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the second O site, O(2) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent Fe(1) atoms to form a mixture of distorted edge and corner-sharing ONa4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 2-15°. In the third O site, O(3) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent Fe(1) atoms to form a mixture of distorted edge and corner-sharing ONa4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 2-15°.
Na2FeO3 is Caswellsilverite-like structured and crystallizes in the monoclinic C2/c space group. There are two inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent Na(2)O6 octahedra, corners with two equivalent Fe(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, edges with five equivalent Na(2)O6 octahedra, and edges with five equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-18°. Both Na(1)-O(1) bond lengths are 2.34 Å. There is one shorter (2.26 Å) and one longer (2.35 Å) Na(1)-O(2) bond length. There is one shorter (2.27 Å) and one longer (2.36 Å) Na(1)-O(3) bond length. In the second Na site, Na(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted NaO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Fe(1)O6 octahedra, edges with three equivalent Na(2)O6 octahedra, edges with four equivalent Fe(1)O6 octahedra, and edges with five equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 16-17°. Both Na(2)-O(1) bond lengths are 2.36 Å. There is one shorter (2.24 Å) and one longer (2.39 Å) Na(2)-O(2) bond length. There is one shorter (2.24 Å) and one longer (2.38 Å) Na(2)-O(3) bond length. Fe(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted FeO6 octahedra that share corners with two equivalent Na(1)O6 octahedra, corners with four equivalent Na(2)O6 octahedra, edges with three equivalent Fe(1)O6 octahedra, edges with four equivalent Na(2)O6 octahedra, and edges with five equivalent Na(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-16°. Both Fe(1)-O(1) bond lengths are 1.93 Å. There is one shorter (1.81 Å) and one longer (2.29 Å) Fe(1)-O(2) bond length. There is one shorter (1.82 Å) and one longer (2.26 Å) Fe(1)-O(3) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent Fe(1) atoms to form a mixture of distorted edge and corner-sharing ONa4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 2-10°. In the second O site, O(2) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent Fe(1) atoms to form a mixture of distorted edge and corner-sharing ONa4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 2-15°. In the third O site, O(3) is bonded to two equivalent Na(1), two equivalent Na(2), and two equivalent Fe(1) atoms to form a mixture of distorted edge and corner-sharing ONa4Fe2 octahedra. The corner-sharing octahedral tilt angles range from 2-15°.