NaV2O5 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with two equivalent V(2)O5 trigonal bipyramids, edges with two equivalent Na(1)O6 octahedra, and edges with two equivalent V(2)O5 trigonal bipyramids. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(5), and three equivalent O(2) atoms. In the second V site, V(2) is bonded to one O(4), one O(5), and three equivalent O(3) atoms to form distorted VO5 trigonal bipyramids that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent V(2)O5 trigonal bipyramids, edges with two equivalent Na(1)O6 octahedra, and edges with two equivalent V(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-57°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one V(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to three equivalent V(1) atoms. In the third O site, O(3) is bonded to one Na(1) and three equivalent V(2) atoms to form a mixture of distorted corner and edge-sharing ONaV3 tetrahedra. In the fourth O site, O(4) is bonded in a linear geometry to one Na(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Na(1), one V(1), and one V(2) atom.
NaV2O5 crystallizes in the orthorhombic Pnma space group. Na(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(5) atoms to form distorted NaO6 octahedra that share corners with two equivalent V(2)O5 trigonal bipyramids, edges with two equivalent Na(1)O6 octahedra, and edges with two equivalent V(2)O5 trigonal bipyramids. The Na(1)-O(3) bond length is 2.42 Å. The Na(1)-O(4) bond length is 2.25 Å. Both Na(1)-O(1) bond lengths are 2.37 Å. Both Na(1)-O(5) bond lengths are 2.44 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded in a 5-coordinate geometry to one O(1), one O(5), and three equivalent O(2) atoms. The V(1)-O(1) bond length is 1.63 Å. The V(1)-O(5) bond length is 1.80 Å. There are two shorter (1.91 Å) and one longer (1.96 Å) V(1)-O(2) bond length. In the second V site, V(2) is bonded to one O(4), one O(5), and three equivalent O(3) atoms to form distorted VO5 trigonal bipyramids that share corners with two equivalent Na(1)O6 octahedra, corners with two equivalent V(2)O5 trigonal bipyramids, edges with two equivalent Na(1)O6 octahedra, and edges with two equivalent V(2)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 2-57°. The V(2)-O(4) bond length is 1.62 Å. The V(2)-O(5) bond length is 1.85 Å. There are two shorter (1.94 Å) and one longer (1.96 Å) V(2)-O(3) bond length. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Na(1) and one V(1) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to three equivalent V(1) atoms. In the third O site, O(3) is bonded to one Na(1) and three equivalent V(2) atoms to form a mixture of distorted corner and edge-sharing ONaV3 tetrahedra. In the fourth O site, O(4) is bonded in a linear geometry to one Na(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to two equivalent Na(1), one V(1), and one V(2) atom.