NaV5O8 crystallizes in the monoclinic C2 space group. Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NaO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, and edges with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-24°. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(4), two equivalent O(2), and three equivalent O(1) atoms to form VO6 octahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Na(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-23°. In the second V site, V(2) is bonded to one O(2), two equivalent O(4), and three equivalent O(3) atoms to form VO6 octahedra that share  a cornercorner with one Na(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent V(3)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-24°. In the third V site, V(3) is bonded to two equivalent O(4) and four equivalent O(3) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 9-23°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1) and three equivalent V(1) atoms to form a mixture of edge and corner-sharing ONa2V3 square pyramids. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Na(1), one V(2), and two equivalent V(1) atoms. In the third O site, O(3) is bonded to two equivalent V(3) and three equivalent V(2) atoms to form a mixture of edge and corner-sharing OV5 square pyramids. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one V(1), one V(3), and two equivalent V(2) atoms.
NaV5O8 crystallizes in the monoclinic C2 space group. Na(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form NaO6 octahedra that share corners with two equivalent V(2)O6 octahedra, corners with four equivalent V(1)O6 octahedra, edges with two equivalent Na(1)O6 octahedra, and edges with six equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-24°. Both Na(1)-O(2) bond lengths are 2.30 Å. There are two shorter (2.35 Å) and two longer (2.36 Å) Na(1)-O(1) bond lengths. There are three inequivalent V sites. In the first V site, V(1) is bonded to one O(4), two equivalent O(2), and three equivalent O(1) atoms to form VO6 octahedra that share  a cornercorner with one V(3)O6 octahedra, corners with two equivalent Na(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with three equivalent Na(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 11-23°. The V(1)-O(4) bond length is 2.15 Å. There is one shorter (1.95 Å) and one longer (2.08 Å) V(1)-O(2) bond length. There are a spread of V(1)-O(1) bond distances ranging from 1.98-2.13 Å. In the second V site, V(2) is bonded to one O(2), two equivalent O(4), and three equivalent O(3) atoms to form VO6 octahedra that share  a cornercorner with one Na(1)O6 octahedra, corners with two equivalent V(3)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent V(3)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-24°. The V(2)-O(2) bond length is 1.94 Å. There is one shorter (1.99 Å) and one longer (2.03 Å) V(2)-O(4) bond length. There are a spread of V(2)-O(3) bond distances ranging from 2.15-2.19 Å. In the third V site, V(3) is bonded to two equivalent O(4) and four equivalent O(3) atoms to form a mixture of edge and corner-sharing VO6 octahedra. The corner-sharing octahedral tilt angles range from 9-23°. Both V(3)-O(4) bond lengths are 2.14 Å. There are two shorter (2.17 Å) and two longer (2.19 Å) V(3)-O(3) bond lengths. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1) and three equivalent V(1) atoms to form a mixture of edge and corner-sharing ONa2V3 square pyramids. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Na(1), one V(2), and two equivalent V(1) atoms. In the third O site, O(3) is bonded to two equivalent V(3) and three equivalent V(2) atoms to form a mixture of edge and corner-sharing OV5 square pyramids. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one V(1), one V(3), and two equivalent V(2) atoms.