NaV2O5 crystallizes in the monoclinic C2/c space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(10), two equivalent O(3), and two equivalent O(9) atoms. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(10), two equivalent O(4), and two equivalent O(9) atoms. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(5), two equivalent O(7), and two equivalent O(8) atoms. In the fourth Na site, Na(4) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(6), two equivalent O(7), and two equivalent O(8) atoms. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(8), and two equivalent O(4) 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(2), one O(5), one O(9), and two equivalent O(6) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. In the third V site, V(3) is bonded to one O(1), one O(4), one O(7), and two equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. In the fourth V site, V(4) is bonded to one O(10), one O(2), one O(6), and two equivalent O(5) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. There are ten inequivalent O sites. In the first O site, O(5) is bonded in a 4-coordinate geometry to one Na(3), one V(2), and two equivalent V(4) atoms. In the second O site, O(6) is bonded in a 4-coordinate geometry to one Na(4), one V(4), and two equivalent V(2) atoms. In the third O site, O(7) is bonded in a distorted single-bond geometry to one Na(3), one Na(4), and one V(3) atom. In the fourth O site, O(8) is bonded in a distorted single-bond geometry to one Na(3), one Na(4), and one V(1) atom. In the fifth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one V(3), and two equivalent V(1) atoms. In the sixth O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one V(1), and one V(3) atom. In the seventh O site, O(9) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), and one V(2) atom. In the eighth O site, O(10) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), and one V(4) atom. In the ninth O site, O(2) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one V(2), and one V(4) atom. In the tenth O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one V(1), and two equivalent V(3) atoms.
NaV2O5 crystallizes in the monoclinic C2/c space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(10), two equivalent O(3), and two equivalent O(9) atoms. Both Na(1)-O(1) bond lengths are 2.47 Å. Both Na(1)-O(10) bond lengths are 2.63 Å. Both Na(1)-O(3) bond lengths are 2.72 Å. Both Na(1)-O(9) bond lengths are 2.56 Å. In the second Na site, Na(2) is bonded in a 8-coordinate geometry to two equivalent O(1), two equivalent O(10), two equivalent O(4), and two equivalent O(9) atoms. Both Na(2)-O(1) bond lengths are 2.49 Å. Both Na(2)-O(10) bond lengths are 2.61 Å. Both Na(2)-O(4) bond lengths are 2.67 Å. Both Na(2)-O(9) bond lengths are 2.56 Å. In the third Na site, Na(3) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(5), two equivalent O(7), and two equivalent O(8) atoms. Both Na(3)-O(2) bond lengths are 2.47 Å. Both Na(3)-O(5) bond lengths are 2.72 Å. Both Na(3)-O(7) bond lengths are 2.61 Å. Both Na(3)-O(8) bond lengths are 2.54 Å. In the fourth Na site, Na(4) is bonded in a 8-coordinate geometry to two equivalent O(2), two equivalent O(6), two equivalent O(7), and two equivalent O(8) atoms. Both Na(4)-O(2) bond lengths are 2.49 Å. Both Na(4)-O(6) bond lengths are 2.67 Å. Both Na(4)-O(7) bond lengths are 2.63 Å. Both Na(4)-O(8) bond lengths are 2.56 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to one O(1), one O(3), one O(8), and two equivalent O(4) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. The V(1)-O(1) bond length is 1.95 Å. The V(1)-O(3) bond length is 1.98 Å. The V(1)-O(8) bond length is 1.66 Å. There is one shorter (1.99 Å) and one longer (2.01 Å) V(1)-O(4) bond length. In the second V site, V(2) is bonded to one O(2), one O(5), one O(9), and two equivalent O(6) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. The V(2)-O(2) bond length is 1.96 Å. The V(2)-O(5) bond length is 1.97 Å. The V(2)-O(9) bond length is 1.66 Å. There is one shorter (1.99 Å) and one longer (2.01 Å) V(2)-O(6) bond length. In the third V site, V(3) is bonded to one O(1), one O(4), one O(7), and two equivalent O(3) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. The V(3)-O(1) bond length is 1.78 Å. The V(3)-O(4) bond length is 1.91 Å. The V(3)-O(7) bond length is 1.64 Å. There is one shorter (1.90 Å) and one longer (2.04 Å) V(3)-O(3) bond length. In the fourth V site, V(4) is bonded to one O(10), one O(2), one O(6), and two equivalent O(5) atoms to form a mixture of distorted corner and edge-sharing VO5 trigonal bipyramids. The V(4)-O(10) bond length is 1.65 Å. The V(4)-O(2) bond length is 1.78 Å. The V(4)-O(6) bond length is 1.91 Å. There is one shorter (1.90 Å) and one longer (2.03 Å) V(4)-O(5) bond length. There are ten inequivalent O sites. In the first O site, O(5) is bonded in a 4-coordinate geometry to one Na(3), one V(2), and two equivalent V(4) atoms. In the second O site, O(6) is bonded in a 4-coordinate geometry to one Na(4), one V(4), and two equivalent V(2) atoms. In the third O site, O(7) is bonded in a distorted single-bond geometry to one Na(3), one Na(4), and one V(3) atom. In the fourth O site, O(8) is bonded in a distorted single-bond geometry to one Na(3), one Na(4), and one V(1) atom. In the fifth O site, O(4) is bonded in a 4-coordinate geometry to one Na(2), one V(3), and two equivalent V(1) atoms. In the sixth O site, O(1) is bonded in a 4-coordinate geometry to one Na(1), one Na(2), one V(1), and one V(3) atom. In the seventh O site, O(9) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), and one V(2) atom. In the eighth O site, O(10) is bonded in a distorted single-bond geometry to one Na(1), one Na(2), and one V(4) atom. In the ninth O site, O(2) is bonded in a 4-coordinate geometry to one Na(3), one Na(4), one V(2), and one V(4) atom. In the tenth O site, O(3) is bonded in a 4-coordinate geometry to one Na(1), one V(1), and two equivalent V(3) atoms.