Na5VO5 crystallizes in the orthorhombic Pbcm space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted NaO4 trigonal pyramids that share corners with six equivalent Na(2)O5 square pyramids, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent Na(1)O4 trigonal pyramids, and edges with two equivalent Na(4)O5 trigonal bipyramids. In the second Na site, Na(2) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form distorted NaO5 square pyramids that share corners with two equivalent Na(2)O5 square pyramids, corners with two equivalent V(1)O4 tetrahedra,  a cornercorner with one Na(4)O5 trigonal bipyramid, corners with three equivalent Na(1)O4 trigonal pyramids, edges with three equivalent Na(2)O5 square pyramids,  an edgeedge with one V(1)O4 tetrahedra, and edges with two equivalent Na(4)O5 trigonal bipyramids. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(1) and four equivalent O(2) atoms. In the fourth Na site, Na(4) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form NaO5 trigonal bipyramids that share corners with two equivalent Na(2)O5 square pyramids, corners with four equivalent V(1)O4 tetrahedra, edges with four equivalent Na(2)O5 square pyramids, and edges with two equivalent Na(1)O4 trigonal pyramids. V(1) is bonded to one O(3), one O(4), and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with four equivalent Na(2)O5 square pyramids, corners with four equivalent Na(4)O5 trigonal bipyramids, corners with two equivalent Na(1)O4 trigonal pyramids, and edges with two equivalent Na(2)O5 square pyramids. There are four inequivalent O sites. In the first O site, O(3) is bonded to one Na(4), four equivalent Na(2), and one V(1) atom to form distorted ONa5V octahedra that share corners with three equivalent O(1)Na6 octahedra,  an edgeedge with one O(1)Na6 octahedra, edges with two equivalent O(3)Na5V octahedra, and edges with four equivalent O(2)Na5V octahedra. The corner-sharing octahedral tilt angles range from 2-15°. In the second O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(4), two equivalent Na(2), and one V(1) atom. In the third O site, O(1) is bonded to one Na(3), one Na(4), two equivalent Na(1), and two equivalent Na(2) atoms to form ONa6 octahedra that share corners with two equivalent O(1)Na6 octahedra, corners with three equivalent O(3)Na5V octahedra, corners with four equivalent O(2)Na5V octahedra,  an edgeedge with one O(3)Na5V octahedra, and edges with four equivalent O(2)Na5V octahedra. The corner-sharing octahedral tilt angles range from 2-54°. In the fourth O site, O(2) is bonded to one Na(1), one Na(2), one Na(4), two equivalent Na(3), and one V(1) atom to form distorted ONa5V octahedra that share corners with two equivalent O(2)Na5V octahedra, corners with two equivalent O(1)Na6 octahedra, edges with two equivalent O(2)Na5V octahedra, edges with two equivalent O(3)Na5V octahedra, edges with two equivalent O(1)Na6 octahedra, and  a faceface with one O(2)Na5V octahedra. The corner-sharing octahedral tilt angles range from 49-54°.
Na5VO5 crystallizes in the orthorhombic Pbcm space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted NaO4 trigonal pyramids that share corners with six equivalent Na(2)O5 square pyramids, corners with two equivalent V(1)O4 tetrahedra, corners with two equivalent Na(1)O4 trigonal pyramids, and edges with two equivalent Na(4)O5 trigonal bipyramids. Both Na(1)-O(1) bond lengths are 2.29 Å. Both Na(1)-O(2) bond lengths are 2.48 Å. In the second Na site, Na(2) is bonded to one O(1), one O(2), one O(4), and two equivalent O(3) atoms to form distorted NaO5 square pyramids that share corners with two equivalent Na(2)O5 square pyramids, corners with two equivalent V(1)O4 tetrahedra,  a cornercorner with one Na(4)O5 trigonal bipyramid, corners with three equivalent Na(1)O4 trigonal pyramids, edges with three equivalent Na(2)O5 square pyramids,  an edgeedge with one V(1)O4 tetrahedra, and edges with two equivalent Na(4)O5 trigonal bipyramids. The Na(2)-O(1) bond length is 2.31 Å. The Na(2)-O(2) bond length is 2.50 Å. The Na(2)-O(4) bond length is 2.48 Å. There is one shorter (2.44 Å) and one longer (2.53 Å) Na(2)-O(3) bond length. In the third Na site, Na(3) is bonded in a 5-coordinate geometry to one O(1) and four equivalent O(2) atoms. The Na(3)-O(1) bond length is 2.26 Å. There are two shorter (2.49 Å) and two longer (2.54 Å) Na(3)-O(2) bond lengths. In the fourth Na site, Na(4) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form NaO5 trigonal bipyramids that share corners with two equivalent Na(2)O5 square pyramids, corners with four equivalent V(1)O4 tetrahedra, edges with four equivalent Na(2)O5 square pyramids, and edges with two equivalent Na(1)O4 trigonal pyramids. The Na(4)-O(1) bond length is 2.34 Å. The Na(4)-O(3) bond length is 2.65 Å. The Na(4)-O(4) bond length is 2.48 Å. Both Na(4)-O(2) bond lengths are 2.44 Å. V(1) is bonded to one O(3), one O(4), and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with four equivalent Na(2)O5 square pyramids, corners with four equivalent Na(4)O5 trigonal bipyramids, corners with two equivalent Na(1)O4 trigonal pyramids, and edges with two equivalent Na(2)O5 square pyramids. The V(1)-O(3) bond length is 1.74 Å. The V(1)-O(4) bond length is 1.75 Å. Both V(1)-O(2) bond lengths are 1.75 Å. There are four inequivalent O sites. In the first O site, O(3) is bonded to one Na(4), four equivalent Na(2), and one V(1) atom to form distorted ONa5V octahedra that share corners with three equivalent O(1)Na6 octahedra,  an edgeedge with one O(1)Na6 octahedra, edges with two equivalent O(3)Na5V octahedra, and edges with four equivalent O(2)Na5V octahedra. The corner-sharing octahedral tilt angles range from 2-15°. In the second O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Na(4), two equivalent Na(2), and one V(1) atom. In the third O site, O(1) is bonded to one Na(3), one Na(4), two equivalent Na(1), and two equivalent Na(2) atoms to form ONa6 octahedra that share corners with two equivalent O(1)Na6 octahedra, corners with three equivalent O(3)Na5V octahedra, corners with four equivalent O(2)Na5V octahedra,  an edgeedge with one O(3)Na5V octahedra, and edges with four equivalent O(2)Na5V octahedra. The corner-sharing octahedral tilt angles range from 2-54°. In the fourth O site, O(2) is bonded to one Na(1), one Na(2), one Na(4), two equivalent Na(3), and one V(1) atom to form distorted ONa5V octahedra that share corners with two equivalent O(2)Na5V octahedra, corners with two equivalent O(1)Na6 octahedra, edges with two equivalent O(2)Na5V octahedra, edges with two equivalent O(3)Na5V octahedra, edges with two equivalent O(1)Na6 octahedra, and  a faceface with one O(2)Na5V octahedra. The corner-sharing octahedral tilt angles range from 49-54°.