Na3FeO3 is Aluminum carbonitride-like structured and crystallizes in the monoclinic Cc space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(3), two equivalent O(2), and two equivalent O(6) atoms to form distorted NaO5 trigonal bipyramids that share  a cornercorner with one Fe(2)O4 tetrahedra, corners with two equivalent Fe(1)O4 tetrahedra, corners with two equivalent Na(6)O4 trigonal pyramids,  an edgeedge with one Fe(1)O4 tetrahedra,  an edgeedge with one Fe(2)O4 tetrahedra, and edges with two equivalent Na(1)O5 trigonal bipyramids. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(4), and one O(6) atom. In the third Na site, Na(3) is bonded to two equivalent O(4) and two equivalent O(5) atoms to form distorted NaO4 trigonal pyramids that share corners with two equivalent Fe(1)O4 tetrahedra, corners with two equivalent Fe(2)O4 tetrahedra, corners with two equivalent Na(6)O4 trigonal pyramids, and edges with two equivalent Na(3)O4 trigonal pyramids. In the fourth Na site, Na(4) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(5), and two equivalent O(6) atoms. In the fifth Na site, Na(5) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(3), one O(4), and one O(5) atom. In the sixth Na site, Na(6) is bonded to one O(1), one O(4), and two equivalent O(3) atoms to form distorted NaO4 trigonal pyramids that share corners with three equivalent Fe(2)O4 tetrahedra, corners with two equivalent Na(1)O5 trigonal bipyramids, corners with two equivalent Na(3)O4 trigonal pyramids, corners with two equivalent Na(6)O4 trigonal pyramids, and  an edgeedge with one Fe(1)O4 tetrahedra. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form FeO4 tetrahedra that share corners with two equivalent Fe(2)O4 tetrahedra, corners with two equivalent Na(1)O5 trigonal bipyramids, corners with two equivalent Na(3)O4 trigonal pyramids,  an edgeedge with one Na(1)O5 trigonal bipyramid, and  an edgeedge with one Na(6)O4 trigonal pyramid. In the second Fe site, Fe(2) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form FeO4 tetrahedra that share corners with two equivalent Fe(1)O4 tetrahedra,  a cornercorner with one Na(1)O5 trigonal bipyramid, corners with two equivalent Na(3)O4 trigonal pyramids, corners with three equivalent Na(6)O4 trigonal pyramids, and  an edgeedge with one Na(1)O5 trigonal bipyramid. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(4), one Na(5), one Na(6), one Fe(1), and one Fe(2) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(1), one Fe(1), and one Fe(2) atom. In the third O site, O(3) is bonded to one Na(1), one Na(2), one Na(5), two equivalent Na(6), and one Fe(2) atom to form a mixture of corner and edge-sharing ONa5Fe octahedra. The corner-sharing octahedral tilt angles range from 47-55°. In the fourth O site, O(4) is bonded to one Na(2), one Na(5), one Na(6), two equivalent Na(3), and one Fe(1) atom to form a mixture of corner and edge-sharing ONa5Fe octahedra. The corner-sharing octahedral tilt angles range from 47-54°. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Na(5), two equivalent Na(3), two equivalent Na(4), and one Fe(2) atom. In the sixth O site, O(6) is bonded in a 6-coordinate geometry to one Na(2), two equivalent Na(1), two equivalent Na(4), and one Fe(1) atom.
Na3FeO3 is Aluminum carbonitride-like structured and crystallizes in the monoclinic Cc space group. There are six inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(3), two equivalent O(2), and two equivalent O(6) atoms to form distorted NaO5 trigonal bipyramids that share  a cornercorner with one Fe(2)O4 tetrahedra, corners with two equivalent Fe(1)O4 tetrahedra, corners with two equivalent Na(6)O4 trigonal pyramids,  an edgeedge with one Fe(1)O4 tetrahedra,  an edgeedge with one Fe(2)O4 tetrahedra, and edges with two equivalent Na(1)O5 trigonal bipyramids. The Na(1)-O(3) bond length is 2.37 Å. There is one shorter (2.51 Å) and one longer (2.66 Å) Na(1)-O(2) bond length. There is one shorter (2.32 Å) and one longer (2.33 Å) Na(1)-O(6) bond length. In the second Na site, Na(2) is bonded in a 4-coordinate geometry to one O(2), one O(3), one O(4), and one O(6) atom. The Na(2)-O(2) bond length is 2.32 Å. The Na(2)-O(3) bond length is 2.43 Å. The Na(2)-O(4) bond length is 2.43 Å. The Na(2)-O(6) bond length is 2.41 Å. In the third Na site, Na(3) is bonded to two equivalent O(4) and two equivalent O(5) atoms to form distorted NaO4 trigonal pyramids that share corners with two equivalent Fe(1)O4 tetrahedra, corners with two equivalent Fe(2)O4 tetrahedra, corners with two equivalent Na(6)O4 trigonal pyramids, and edges with two equivalent Na(3)O4 trigonal pyramids. There is one shorter (2.21 Å) and one longer (2.28 Å) Na(3)-O(4) bond length. There is one shorter (2.35 Å) and one longer (2.39 Å) Na(3)-O(5) bond length. In the fourth Na site, Na(4) is bonded in a 5-coordinate geometry to one O(1), two equivalent O(5), and two equivalent O(6) atoms. The Na(4)-O(1) bond length is 2.61 Å. There is one shorter (2.32 Å) and one longer (2.39 Å) Na(4)-O(5) bond length. There is one shorter (2.25 Å) and one longer (2.62 Å) Na(4)-O(6) bond length. In the fifth Na site, Na(5) is bonded in a distorted rectangular see-saw-like geometry to one O(1), one O(3), one O(4), and one O(5) atom. The Na(5)-O(1) bond length is 2.30 Å. The Na(5)-O(3) bond length is 2.36 Å. The Na(5)-O(4) bond length is 2.39 Å. The Na(5)-O(5) bond length is 2.44 Å. In the sixth Na site, Na(6) is bonded to one O(1), one O(4), and two equivalent O(3) atoms to form distorted NaO4 trigonal pyramids that share corners with three equivalent Fe(2)O4 tetrahedra, corners with two equivalent Na(1)O5 trigonal bipyramids, corners with two equivalent Na(3)O4 trigonal pyramids, corners with two equivalent Na(6)O4 trigonal pyramids, and  an edgeedge with one Fe(1)O4 tetrahedra. The Na(6)-O(1) bond length is 2.40 Å. The Na(6)-O(4) bond length is 2.33 Å. There is one shorter (2.27 Å) and one longer (2.28 Å) Na(6)-O(3) bond length. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), one O(4), and one O(6) atom to form FeO4 tetrahedra that share corners with two equivalent Fe(2)O4 tetrahedra, corners with two equivalent Na(1)O5 trigonal bipyramids, corners with two equivalent Na(3)O4 trigonal pyramids,  an edgeedge with one Na(1)O5 trigonal bipyramid, and  an edgeedge with one Na(6)O4 trigonal pyramid. The Fe(1)-O(1) bond length is 1.94 Å. The Fe(1)-O(2) bond length is 1.91 Å. The Fe(1)-O(4) bond length is 1.85 Å. The Fe(1)-O(6) bond length is 1.84 Å. In the second Fe site, Fe(2) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form FeO4 tetrahedra that share corners with two equivalent Fe(1)O4 tetrahedra,  a cornercorner with one Na(1)O5 trigonal bipyramid, corners with two equivalent Na(3)O4 trigonal pyramids, corners with three equivalent Na(6)O4 trigonal pyramids, and  an edgeedge with one Na(1)O5 trigonal bipyramid. The Fe(2)-O(1) bond length is 1.91 Å. The Fe(2)-O(2) bond length is 1.93 Å. The Fe(2)-O(3) bond length is 1.86 Å. The Fe(2)-O(5) bond length is 1.87 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 5-coordinate geometry to one Na(4), one Na(5), one Na(6), one Fe(1), and one Fe(2) atom. In the second O site, O(2) is bonded in a 5-coordinate geometry to one Na(2), two equivalent Na(1), one Fe(1), and one Fe(2) atom. In the third O site, O(3) is bonded to one Na(1), one Na(2), one Na(5), two equivalent Na(6), and one Fe(2) atom to form a mixture of corner and edge-sharing ONa5Fe octahedra. The corner-sharing octahedral tilt angles range from 47-55°. In the fourth O site, O(4) is bonded to one Na(2), one Na(5), one Na(6), two equivalent Na(3), and one Fe(1) atom to form a mixture of corner and edge-sharing ONa5Fe octahedra. The corner-sharing octahedral tilt angles range from 47-54°. In the fifth O site, O(5) is bonded in a 6-coordinate geometry to one Na(5), two equivalent Na(3), two equivalent Na(4), and one Fe(2) atom. In the sixth O site, O(6) is bonded in a 6-coordinate geometry to one Na(2), two equivalent Na(1), two equivalent Na(4), and one Fe(1) atom.