NaV2O5 crystallizes in the orthorhombic Pmmn space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), and four equivalent O(3) atoms. V(1) is bonded to one O(1), one O(3), and three equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. 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 trigonal pyramids. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1) and three equivalent V(1) atoms. In the third O site, O(3) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one V(1) atom.
NaV2O5 crystallizes in the orthorhombic Pmmn space group. Na(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(2), and four equivalent O(3) atoms. Both Na(1)-O(1) bond lengths are 2.43 Å. Both Na(1)-O(2) bond lengths are 2.61 Å. All Na(1)-O(3) bond lengths are 2.52 Å. V(1) is bonded to one O(1), one O(3), and three equivalent O(2) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. The V(1)-O(1) bond length is 1.81 Å. The V(1)-O(3) bond length is 1.63 Å. There are two shorter (1.91 Å) and one longer (1.98 Å) V(1)-O(2) bond length. 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 trigonal pyramids. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Na(1) and three equivalent V(1) atoms. In the third O site, O(3) is bonded in a distorted single-bond geometry to two equivalent Na(1) and one V(1) atom.