Na2FeO3 crystallizes in the orthorhombic Cmc2_1 space group. Na(1) is bonded to one O(2) and four equivalent O(1) atoms to form distorted NaO5 trigonal bipyramids that share corners with four equivalent Fe(1)O4 tetrahedra, corners with five equivalent Na(1)O5 trigonal bipyramids,  an edgeedge with one Fe(1)O4 tetrahedra, and edges with four equivalent Na(1)O5 trigonal bipyramids. Fe(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form FeO4 tetrahedra that share corners with two equivalent Fe(1)O4 tetrahedra, corners with eight equivalent Na(1)O5 trigonal bipyramids, and edges with two equivalent Na(1)O5 trigonal bipyramids. There are two inequivalent O sites. In the first O site, O(1) is bonded to four equivalent Na(1) and one Fe(1) atom to form distorted ONa4Fe trigonal bipyramids that share corners with four equivalent O(2)Na2Fe2 tetrahedra, corners with five equivalent O(1)Na4Fe trigonal bipyramids,  an edgeedge with one O(2)Na2Fe2 tetrahedra, and edges with four equivalent O(1)Na4Fe trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Na(1) and two equivalent Fe(1) atoms to form ONa2Fe2 tetrahedra that share corners with two equivalent O(2)Na2Fe2 tetrahedra, corners with eight equivalent O(1)Na4Fe trigonal bipyramids, and edges with two equivalent O(1)Na4Fe trigonal bipyramids.
Na2FeO3 crystallizes in the orthorhombic Cmc2_1 space group. Na(1) is bonded to one O(2) and four equivalent O(1) atoms to form distorted NaO5 trigonal bipyramids that share corners with four equivalent Fe(1)O4 tetrahedra, corners with five equivalent Na(1)O5 trigonal bipyramids,  an edgeedge with one Fe(1)O4 tetrahedra, and edges with four equivalent Na(1)O5 trigonal bipyramids. The Na(1)-O(2) bond length is 2.35 Å. There are a spread of Na(1)-O(1) bond distances ranging from 2.33-2.68 Å. Fe(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form FeO4 tetrahedra that share corners with two equivalent Fe(1)O4 tetrahedra, corners with eight equivalent Na(1)O5 trigonal bipyramids, and edges with two equivalent Na(1)O5 trigonal bipyramids. Both Fe(1)-O(1) bond lengths are 1.78 Å. There is one shorter (1.86 Å) and one longer (1.92 Å) Fe(1)-O(2) bond length. There are two inequivalent O sites. In the first O site, O(1) is bonded to four equivalent Na(1) and one Fe(1) atom to form distorted ONa4Fe trigonal bipyramids that share corners with four equivalent O(2)Na2Fe2 tetrahedra, corners with five equivalent O(1)Na4Fe trigonal bipyramids,  an edgeedge with one O(2)Na2Fe2 tetrahedra, and edges with four equivalent O(1)Na4Fe trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Na(1) and two equivalent Fe(1) atoms to form ONa2Fe2 tetrahedra that share corners with two equivalent O(2)Na2Fe2 tetrahedra, corners with eight equivalent O(1)Na4Fe trigonal bipyramids, and edges with two equivalent O(1)Na4Fe trigonal bipyramids.