Na5VO4 crystallizes in the orthorhombic Pmmn space group. There are two 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 NaO4 tetrahedra that share corners with four equivalent V(1)O4 tetrahedra, corners with eight equivalent Na(2)O4 tetrahedra, and edges with four equivalent Na(2)O4 tetrahedra. In the second Na site, Na(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted NaO4 tetrahedra that share corners with two equivalent Na(1)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with eight equivalent Na(2)O4 tetrahedra,  an edgeedge with one Na(1)O4 tetrahedra,  an edgeedge with one V(1)O4 tetrahedra, and edges with two equivalent Na(2)O4 tetrahedra. V(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with four equivalent Na(1)O4 tetrahedra, corners with eight equivalent Na(2)O4 tetrahedra, and edges with four equivalent Na(2)O4 tetrahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), four equivalent Na(2), and one V(1) atom to form a mixture of distorted corner and edge-sharing ONa5V octahedra. The corner-sharing octahedral tilt angles range from 59-65°. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Na(1), four equivalent Na(2), and one V(1) atom.
Na5VO4 crystallizes in the orthorhombic Pmmn space group. There are two 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 NaO4 tetrahedra that share corners with four equivalent V(1)O4 tetrahedra, corners with eight equivalent Na(2)O4 tetrahedra, and edges with four equivalent Na(2)O4 tetrahedra. Both Na(1)-O(1) bond lengths are 2.41 Å. Both Na(1)-O(2) bond lengths are 2.34 Å. In the second Na site, Na(2) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted NaO4 tetrahedra that share corners with two equivalent Na(1)O4 tetrahedra, corners with two equivalent V(1)O4 tetrahedra, corners with eight equivalent Na(2)O4 tetrahedra,  an edgeedge with one Na(1)O4 tetrahedra,  an edgeedge with one V(1)O4 tetrahedra, and edges with two equivalent Na(2)O4 tetrahedra. There is one shorter (2.35 Å) and one longer (2.37 Å) Na(2)-O(1) bond length. There is one shorter (2.34 Å) and one longer (2.46 Å) Na(2)-O(2) bond length. V(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form VO4 tetrahedra that share corners with four equivalent Na(1)O4 tetrahedra, corners with eight equivalent Na(2)O4 tetrahedra, and edges with four equivalent Na(2)O4 tetrahedra. Both V(1)-O(1) bond lengths are 1.97 Å. Both V(1)-O(2) bond lengths are 1.95 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Na(1), four equivalent Na(2), and one V(1) atom to form a mixture of distorted corner and edge-sharing ONa5V octahedra. The corner-sharing octahedral tilt angles range from 59-65°. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Na(1), four equivalent Na(2), and one V(1) atom.