NaFe3O5 crystallizes in the orthorhombic Pnnm space group. Na(1) is bonded in a 8-coordinate geometry to one O(3), one O(5), two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing FeO6 octahedra. The corner-sharing octahedral tilt angles are 50°. In the second Fe site, Fe(2) is bonded in a 6-coordinate geometry to one O(2), one O(5), two equivalent O(3), and two equivalent O(4) atoms. In the third Fe site, Fe(3) is bonded to two equivalent O(1) and four equivalent O(5) atoms to form edge-sharing FeO6 octahedra. In the fourth Fe site, Fe(4) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form a mixture of corner and edge-sharing FeO6 octahedra. The corner-sharing octahedral tilt angles are 50°. There are five inequivalent O sites. In the first O site, O(5) is bonded to one Na(1), one Fe(1), one Fe(2), and two equivalent Fe(3) atoms to form distorted ONaFe4 trigonal bipyramids that share corners with four equivalent O(5)NaFe4 trigonal bipyramids, edges with four equivalent O(1)Na2Fe3 square pyramids, and  an edgeedge with one O(5)NaFe4 trigonal bipyramid. In the second O site, O(1) is bonded to two equivalent Na(1), one Fe(3), and two equivalent Fe(1) atoms to form ONa2Fe3 square pyramids that share  a cornercorner with one O(1)Na2Fe3 square pyramid, edges with two equivalent O(1)Na2Fe3 square pyramids, and edges with four equivalent O(5)NaFe4 trigonal bipyramids. In the third O site, O(2) is bonded in a 5-coordinate geometry to two equivalent Na(1), one Fe(2), and two equivalent Fe(4) atoms. In the fourth O site, O(3) is bonded in a 6-coordinate geometry to one Na(1), one Fe(4), two equivalent Fe(1), and two equivalent Fe(2) atoms. In the fifth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent Na(1), one Fe(1), and two equivalent Fe(2) atoms.
NaFe3O5 crystallizes in the orthorhombic Pnnm space group. Na(1) is bonded in a 8-coordinate geometry to one O(3), one O(5), two equivalent O(1), two equivalent O(2), and two equivalent O(4) atoms. The Na(1)-O(3) bond length is 2.95 Å. The Na(1)-O(5) bond length is 2.58 Å. Both Na(1)-O(1) bond lengths are 2.41 Å. Both Na(1)-O(2) bond lengths are 2.45 Å. Both Na(1)-O(4) bond lengths are 2.63 Å. There are four inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(4), one O(5), two equivalent O(1), and two equivalent O(3) atoms to form a mixture of corner and edge-sharing FeO6 octahedra. The corner-sharing octahedral tilt angles are 50°. The Fe(1)-O(4) bond length is 2.04 Å. The Fe(1)-O(5) bond length is 2.14 Å. Both Fe(1)-O(1) bond lengths are 2.01 Å. Both Fe(1)-O(3) bond lengths are 2.13 Å. In the second Fe site, Fe(2) is bonded in a 6-coordinate geometry to one O(2), one O(5), two equivalent O(3), and two equivalent O(4) atoms. The Fe(2)-O(2) bond length is 1.95 Å. The Fe(2)-O(5) bond length is 1.99 Å. Both Fe(2)-O(3) bond lengths are 2.45 Å. Both Fe(2)-O(4) bond lengths are 1.99 Å. In the third Fe site, Fe(3) is bonded to two equivalent O(1) and four equivalent O(5) atoms to form edge-sharing FeO6 octahedra. Both Fe(3)-O(1) bond lengths are 2.01 Å. All Fe(3)-O(5) bond lengths are 2.04 Å. In the fourth Fe site, Fe(4) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form a mixture of corner and edge-sharing FeO6 octahedra. The corner-sharing octahedral tilt angles are 50°. Both Fe(4)-O(3) bond lengths are 2.09 Å. All Fe(4)-O(2) bond lengths are 2.05 Å. There are five inequivalent O sites. In the first O site, O(5) is bonded to one Na(1), one Fe(1), one Fe(2), and two equivalent Fe(3) atoms to form distorted ONaFe4 trigonal bipyramids that share corners with four equivalent O(5)NaFe4 trigonal bipyramids, edges with four equivalent O(1)Na2Fe3 square pyramids, and  an edgeedge with one O(5)NaFe4 trigonal bipyramid. In the second O site, O(1) is bonded to two equivalent Na(1), one Fe(3), and two equivalent Fe(1) atoms to form ONa2Fe3 square pyramids that share  a cornercorner with one O(1)Na2Fe3 square pyramid, edges with two equivalent O(1)Na2Fe3 square pyramids, and edges with four equivalent O(5)NaFe4 trigonal bipyramids. In the third O site, O(2) is bonded in a 5-coordinate geometry to two equivalent Na(1), one Fe(2), and two equivalent Fe(4) atoms. In the fourth O site, O(3) is bonded in a 6-coordinate geometry to one Na(1), one Fe(4), two equivalent Fe(1), and two equivalent Fe(2) atoms. In the fifth O site, O(4) is bonded in a 5-coordinate geometry to two equivalent Na(1), one Fe(1), and two equivalent Fe(2) atoms.