Na5V12O32 crystallizes in the monoclinic Cm space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(18), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form edge-sharing NaO6 octahedra. In the second Na site, Na(2) is bonded to one O(19), one O(6), two equivalent O(11), and two equivalent O(9) atoms to form edge-sharing NaO6 octahedra. In the third Na site, Na(3) is bonded to one O(12), one O(13), one O(16), one O(17), one O(20), and one O(8) atom to form NaO6 octahedra that share  a cornercorner with one Na(4)O4 tetrahedra and edges with two equivalent Na(3)O6 octahedra. In the fourth Na site, Na(4) is bonded to one O(12), one O(2), and two equivalent O(22) atoms to form distorted corner-sharing NaO4 tetrahedra. The corner-sharing octahedral tilt angles are 70°. There are nine inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(14), one O(19), one O(2), one O(7), and two equivalent O(1) atoms. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(15), one O(18), one O(3), one O(6), and two equivalent O(1) atoms. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(21), one O(4), one O(5), one O(8), and one O(9) atom. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(12), one O(14), one O(2), one O(23), and two equivalent O(10) atoms. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(13), one O(15), one O(24), one O(3), and two equivalent O(10) atoms. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(11), one O(14), one O(15), and one O(22) atom. In the seventh V site, V(7) is bonded in a 5-coordinate geometry to one O(16), one O(18), one O(4), and two equivalent O(21) atoms. In the eighth V site, V(8) is bonded in a 5-coordinate geometry to one O(17), one O(19), one O(5), and two equivalent O(21) atoms. In the ninth V site, V(9) is bonded in a 6-coordinate geometry to one O(10), one O(20), one O(22), one O(23), one O(24), and one O(8) atom. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(2), and one V(6) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(4), one V(1), and one V(4) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one V(2) and one V(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(7) and two equivalent V(3) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one V(8) and two equivalent V(3) atoms. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Na(2) and one V(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one V(1) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Na(3), one V(3), and one V(9) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one V(3) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one V(4), one V(5), one V(6), and one V(9) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one V(6) atom. In the twelfth O site, O(12) is bonded in a distorted tetrahedral geometry to one Na(4), two equivalent Na(3), and one V(4) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to two equivalent Na(3) and one V(5) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one V(1), one V(4), and two equivalent V(6) atoms. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one V(2), one V(5), and two equivalent V(6) atoms. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to two equivalent Na(3) and one V(7) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal planar geometry to two equivalent Na(3) and one V(8) atom. In the eighteenth O site, O(18) is bonded in a trigonal planar geometry to one Na(1), one V(2), and one V(7) atom. In the nineteenth O site, O(19) is bonded in a trigonal planar geometry to one Na(2), one V(1), and one V(8) atom. In the twentieth O site, O(20) is bonded in a distorted bent 150 degrees geometry to one Na(3) and one V(9) atom. In the twenty-first O site, O(21) is bonded in a distorted trigonal non-coplanar geometry to one V(3), one V(7), and one V(8) atom. In the twenty-second O site, O(22) is bonded in a trigonal non-coplanar geometry to one Na(4), one V(6), and one V(9) atom. In the twenty-third O site, O(23) is bonded in a distorted trigonal non-coplanar geometry to one V(4) and two equivalent V(9) atoms. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one V(5) and two equivalent V(9) atoms.
Na5V12O32 crystallizes in the monoclinic Cm space group. There are four inequivalent Na sites. In the first Na site, Na(1) is bonded to one O(18), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form edge-sharing NaO6 octahedra. The Na(1)-O(18) bond length is 2.47 Å. The Na(1)-O(7) bond length is 2.44 Å. Both Na(1)-O(11) bond lengths are 2.43 Å. Both Na(1)-O(9) bond lengths are 2.44 Å. In the second Na site, Na(2) is bonded to one O(19), one O(6), two equivalent O(11), and two equivalent O(9) atoms to form edge-sharing NaO6 octahedra. The Na(2)-O(19) bond length is 2.49 Å. The Na(2)-O(6) bond length is 2.42 Å. Both Na(2)-O(11) bond lengths are 2.43 Å. Both Na(2)-O(9) bond lengths are 2.45 Å. In the third Na site, Na(3) is bonded to one O(12), one O(13), one O(16), one O(17), one O(20), and one O(8) atom to form NaO6 octahedra that share  a cornercorner with one Na(4)O4 tetrahedra and edges with two equivalent Na(3)O6 octahedra. The Na(3)-O(12) bond length is 2.47 Å. The Na(3)-O(13) bond length is 2.44 Å. The Na(3)-O(16) bond length is 2.45 Å. The Na(3)-O(17) bond length is 2.43 Å. The Na(3)-O(20) bond length is 2.43 Å. The Na(3)-O(8) bond length is 2.48 Å. In the fourth Na site, Na(4) is bonded to one O(12), one O(2), and two equivalent O(22) atoms to form distorted corner-sharing NaO4 tetrahedra. The corner-sharing octahedral tilt angles are 70°. The Na(4)-O(12) bond length is 2.35 Å. The Na(4)-O(2) bond length is 2.31 Å. Both Na(4)-O(22) bond lengths are 2.28 Å. There are nine inequivalent V sites. In the first V site, V(1) is bonded in a 6-coordinate geometry to one O(14), one O(19), one O(2), one O(7), and two equivalent O(1) atoms. The V(1)-O(14) bond length is 2.27 Å. The V(1)-O(19) bond length is 2.01 Å. The V(1)-O(2) bond length is 1.94 Å. The V(1)-O(7) bond length is 1.64 Å. Both V(1)-O(1) bond lengths are 1.91 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to one O(15), one O(18), one O(3), one O(6), and two equivalent O(1) atoms. The V(2)-O(15) bond length is 2.31 Å. The V(2)-O(18) bond length is 2.04 Å. The V(2)-O(3) bond length is 1.89 Å. The V(2)-O(6) bond length is 1.64 Å. Both V(2)-O(1) bond lengths are 1.91 Å. In the third V site, V(3) is bonded in a 5-coordinate geometry to one O(21), one O(4), one O(5), one O(8), and one O(9) atom. The V(3)-O(21) bond length is 2.03 Å. The V(3)-O(4) bond length is 1.92 Å. The V(3)-O(5) bond length is 1.92 Å. The V(3)-O(8) bond length is 1.75 Å. The V(3)-O(9) bond length is 1.65 Å. In the fourth V site, V(4) is bonded in a 6-coordinate geometry to one O(12), one O(14), one O(2), one O(23), and two equivalent O(10) atoms. The V(4)-O(12) bond length is 1.67 Å. The V(4)-O(14) bond length is 2.46 Å. The V(4)-O(2) bond length is 1.78 Å. The V(4)-O(23) bond length is 2.07 Å. Both V(4)-O(10) bond lengths are 1.89 Å. In the fifth V site, V(5) is bonded in a 6-coordinate geometry to one O(13), one O(15), one O(24), one O(3), and two equivalent O(10) atoms. The V(5)-O(13) bond length is 1.65 Å. The V(5)-O(15) bond length is 2.50 Å. The V(5)-O(24) bond length is 2.12 Å. The V(5)-O(3) bond length is 1.77 Å. Both V(5)-O(10) bond lengths are 1.90 Å. In the sixth V site, V(6) is bonded in a 6-coordinate geometry to one O(1), one O(10), one O(11), one O(14), one O(15), and one O(22) atom. The V(6)-O(1) bond length is 2.11 Å. The V(6)-O(10) bond length is 2.50 Å. The V(6)-O(11) bond length is 1.65 Å. The V(6)-O(14) bond length is 1.90 Å. The V(6)-O(15) bond length is 1.90 Å. The V(6)-O(22) bond length is 1.77 Å. In the seventh V site, V(7) is bonded in a 5-coordinate geometry to one O(16), one O(18), one O(4), and two equivalent O(21) atoms. The V(7)-O(16) bond length is 1.65 Å. The V(7)-O(18) bond length is 1.75 Å. The V(7)-O(4) bond length is 2.03 Å. Both V(7)-O(21) bond lengths are 1.92 Å. In the eighth V site, V(8) is bonded in a 5-coordinate geometry to one O(17), one O(19), one O(5), and two equivalent O(21) atoms. The V(8)-O(17) bond length is 1.65 Å. The V(8)-O(19) bond length is 1.76 Å. The V(8)-O(5) bond length is 2.03 Å. Both V(8)-O(21) bond lengths are 1.92 Å. In the ninth V site, V(9) is bonded in a 6-coordinate geometry to one O(10), one O(20), one O(22), one O(23), one O(24), and one O(8) atom. The V(9)-O(10) bond length is 2.28 Å. The V(9)-O(20) bond length is 1.64 Å. The V(9)-O(22) bond length is 1.96 Å. The V(9)-O(23) bond length is 1.91 Å. The V(9)-O(24) bond length is 1.91 Å. The V(9)-O(8) bond length is 2.01 Å. There are twenty-four inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal non-coplanar geometry to one V(1), one V(2), and one V(6) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Na(4), one V(1), and one V(4) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one V(2) and one V(5) atom. In the fourth O site, O(4) is bonded in a distorted trigonal non-coplanar geometry to one V(7) and two equivalent V(3) atoms. In the fifth O site, O(5) is bonded in a distorted trigonal non-coplanar geometry to one V(8) and two equivalent V(3) atoms. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Na(2) and one V(2) atom. In the seventh O site, O(7) is bonded in a distorted bent 150 degrees geometry to one Na(1) and one V(1) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Na(3), one V(3), and one V(9) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one V(3) atom. In the tenth O site, O(10) is bonded in a 4-coordinate geometry to one V(4), one V(5), one V(6), and one V(9) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Na(1), one Na(2), and one V(6) atom. In the twelfth O site, O(12) is bonded in a distorted tetrahedral geometry to one Na(4), two equivalent Na(3), and one V(4) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to two equivalent Na(3) and one V(5) atom. In the fourteenth O site, O(14) is bonded in a 4-coordinate geometry to one V(1), one V(4), and two equivalent V(6) atoms. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one V(2), one V(5), and two equivalent V(6) atoms. In the sixteenth O site, O(16) is bonded in a distorted trigonal planar geometry to two equivalent Na(3) and one V(7) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal planar geometry to two equivalent Na(3) and one V(8) atom. In the eighteenth O site, O(18) is bonded in a trigonal planar geometry to one Na(1), one V(2), and one V(7) atom. In the nineteenth O site, O(19) is bonded in a trigonal planar geometry to one Na(2), one V(1), and one V(8) atom. In the twentieth O site, O(20) is bonded in a distorted bent 150 degrees geometry to one Na(3) and one V(9) atom. In the twenty-first O site, O(21) is bonded in a distorted trigonal non-coplanar geometry to one V(3), one V(7), and one V(8) atom. In the twenty-second O site, O(22) is bonded in a trigonal non-coplanar geometry to one Na(4), one V(6), and one V(9) atom. In the twenty-third O site, O(23) is bonded in a distorted trigonal non-coplanar geometry to one V(4) and two equivalent V(9) atoms. In the twenty-fourth O site, O(24) is bonded in a 3-coordinate geometry to one V(5) and two equivalent V(9) atoms.