Na2V2O5 crystallizes in the orthorhombic Ima2 space group. Na(1) is bonded in a 8-coordinate geometry to one O(1), three equivalent O(3), and four equivalent O(2) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form VO4 tetrahedra that share corners with two equivalent V(2)O6 octahedra and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 38°. In the second V site, V(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 13°. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1) and two equivalent V(1) atoms to form distorted corner-sharing ONa2V2 tetrahedra. In the second O site, O(2) is bonded in a 6-coordinate geometry to four equivalent Na(1) and two equivalent V(2) atoms. In the third O site, O(3) is bonded in a 5-coordinate geometry to three equivalent Na(1), one V(1), and one V(2) atom.
Na2V2O5 crystallizes in the orthorhombic Ima2 space group. Na(1) is bonded in a 8-coordinate geometry to one O(1), three equivalent O(3), and four equivalent O(2) atoms. The Na(1)-O(1) bond length is 2.34 Å. There are a spread of Na(1)-O(3) bond distances ranging from 2.37-2.88 Å. There are a spread of Na(1)-O(2) bond distances ranging from 2.40-2.62 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1) and two equivalent O(3) atoms to form VO4 tetrahedra that share corners with two equivalent V(2)O6 octahedra and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 38°. There is one shorter (1.88 Å) and one longer (1.89 Å) V(1)-O(1) bond length. Both V(1)-O(3) bond lengths are 1.78 Å. In the second V site, V(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form VO6 octahedra that share corners with four equivalent V(2)O6 octahedra and corners with two equivalent V(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 13°. Both V(2)-O(3) bond lengths are 2.07 Å. There are two shorter (1.82 Å) and two longer (2.11 Å) V(2)-O(2) bond lengths. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1) and two equivalent V(1) atoms to form distorted corner-sharing ONa2V2 tetrahedra. In the second O site, O(2) is bonded in a 6-coordinate geometry to four equivalent Na(1) and two equivalent V(2) atoms. In the third O site, O(3) is bonded in a 5-coordinate geometry to three equivalent Na(1), one V(1), and one V(2) atom.