NaV2O5 crystallizes in the orthorhombic Pmn2_1 space group. Na(1) is bonded in a 8-coordinate geometry to one O(2), one O(3), two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(5), and two equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. There are five inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), one V(1), and one V(2) atom to form distorted corner-sharing ONa2V2 tetrahedra. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and two equivalent V(2) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one V(2), and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(1) atom.
NaV2O5 crystallizes in the orthorhombic Pmn2_1 space group. Na(1) is bonded in a 8-coordinate geometry to one O(2), one O(3), two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms. The Na(1)-O(2) bond length is 2.85 Å. The Na(1)-O(3) bond length is 2.60 Å. Both Na(1)-O(1) bond lengths are 2.50 Å. Both Na(1)-O(4) bond lengths are 2.71 Å. Both Na(1)-O(5) bond lengths are 2.49 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(2), one O(5), and two equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. The V(1)-O(1) bond length is 1.96 Å. The V(1)-O(2) bond length is 2.01 Å. The V(1)-O(5) bond length is 1.66 Å. Both V(1)-O(3) bond lengths are 1.97 Å. In the second V site, V(2) is bonded to one O(1), one O(3), one O(4), and two equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. The V(2)-O(1) bond length is 1.78 Å. The V(2)-O(3) bond length is 2.00 Å. The V(2)-O(4) bond length is 1.64 Å. Both V(2)-O(2) bond lengths are 1.93 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Na(1), one V(1), and one V(2) atom to form distorted corner-sharing ONa2V2 tetrahedra. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(1), one V(1), and two equivalent V(2) atoms. In the third O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one V(2), and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one V(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Na(1) and one V(1) atom.