Li5V12O32 crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(18), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form edge-sharing LiO6 octahedra. In the second Li site, Li(2) is bonded to one O(19), one O(6), two equivalent O(11), and two equivalent O(9) atoms to form edge-sharing LiO6 octahedra. In the third Li site, Li(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 LiO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra and edges with two equivalent Li(3)O6 octahedra. In the fourth Li site, Li(4) is bonded to one O(12), one O(2), and two equivalent O(22) atoms to form distorted corner-sharing LiO4 tetrahedra. The corner-sharing octahedral tilt angles are 63°. There are nine inequivalent V sites. In the first V site, V(1) 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 second V site, V(2) 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 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(24), 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(23), 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 distorted T-shaped geometry to one Li(4), one V(2), and one V(4) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one V(1) 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 bent 150 degrees geometry to one Li(2) and one V(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Li(1) and one V(2) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(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 Li(1), one Li(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 Li(1), one Li(2), and one V(6) atom. In the twelfth O site, O(12) is bonded to one Li(4), two equivalent Li(3), and one V(4) atom to form distorted corner-sharing OLi3V tetrahedra. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to two equivalent Li(3) and one V(5) atom. In the fourteenth O site, O(14) is bonded to one V(2), one V(4), and two equivalent V(6) atoms to form distorted corner-sharing OV4 trigonal pyramids. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one V(1), 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 Li(3) and one V(7) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal planar geometry to two equivalent Li(3) and one V(8) atom. In the eighteenth O site, O(18) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(7) atom. In the nineteenth O site, O(19) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one V(8) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one Li(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 Li(4), one V(6), and one V(9) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one V(5) and two equivalent V(9) atoms. In the twenty-fourth O site, O(24) is bonded in a distorted trigonal non-coplanar geometry to one V(4) and two equivalent V(9) atoms.
Li5V12O32 crystallizes in the monoclinic Cm space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(18), one O(7), two equivalent O(11), and two equivalent O(9) atoms to form edge-sharing LiO6 octahedra. The Li(1)-O(18) bond length is 2.08 Å. The Li(1)-O(7) bond length is 2.07 Å. Both Li(1)-O(11) bond lengths are 2.33 Å. Both Li(1)-O(9) bond lengths are 2.32 Å. In the second Li site, Li(2) is bonded to one O(19), one O(6), two equivalent O(11), and two equivalent O(9) atoms to form edge-sharing LiO6 octahedra. The Li(2)-O(19) bond length is 2.10 Å. The Li(2)-O(6) bond length is 2.06 Å. Both Li(2)-O(11) bond lengths are 2.34 Å. Both Li(2)-O(9) bond lengths are 2.32 Å. In the third Li site, Li(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 LiO6 octahedra that share  a cornercorner with one Li(4)O4 tetrahedra and edges with two equivalent Li(3)O6 octahedra. The Li(3)-O(12) bond length is 2.40 Å. The Li(3)-O(13) bond length is 2.33 Å. The Li(3)-O(16) bond length is 2.33 Å. The Li(3)-O(17) bond length is 2.31 Å. The Li(3)-O(20) bond length is 2.07 Å. The Li(3)-O(8) bond length is 2.08 Å. In the fourth Li site, Li(4) is bonded to one O(12), one O(2), and two equivalent O(22) atoms to form distorted corner-sharing LiO4 tetrahedra. The corner-sharing octahedral tilt angles are 63°. The Li(4)-O(12) bond length is 2.14 Å. The Li(4)-O(2) bond length is 1.97 Å. Both Li(4)-O(22) bond lengths are 1.99 Å. There are nine inequivalent V sites. In the first V site, V(1) 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(1)-O(15) bond length is 2.28 Å. The V(1)-O(18) bond length is 2.05 Å. The V(1)-O(3) bond length is 1.89 Å. The V(1)-O(6) 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(14), one O(19), one O(2), one O(7), and two equivalent O(1) atoms. The V(2)-O(14) bond length is 2.30 Å. The V(2)-O(19) bond length is 2.01 Å. The V(2)-O(2) bond length is 1.95 Å. The V(2)-O(7) bond length is 1.64 Å. Both V(2)-O(1) bond lengths are 1.90 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 2.02 Å. The V(3)-O(4) bond length is 1.91 Å. The V(3)-O(5) bond length is 1.92 Å. The V(3)-O(8) bond length is 1.76 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(24), and two equivalent O(10) atoms. The V(4)-O(12) bond length is 1.66 Å. The V(4)-O(14) bond length is 2.35 Å. The V(4)-O(2) bond length is 1.78 Å. The V(4)-O(24) 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(23), one O(3), and two equivalent O(10) atoms. The V(5)-O(13) bond length is 1.64 Å. The V(5)-O(15) bond length is 2.41 Å. The V(5)-O(23) bond length is 2.14 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 2.40 Å. The V(6)-O(11) bond length is 1.64 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 1.78 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 1.76 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 1.77 Å. The V(8)-O(5) bond length is 2.01 Å. Both V(8)-O(21) bond lengths are 1.91 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 2.26 Å. The V(9)-O(20) bond length is 1.64 Å. The V(9)-O(22) bond length is 1.97 Å. The V(9)-O(23) bond length is 1.90 Å. The V(9)-O(24) bond length is 1.90 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 distorted T-shaped geometry to one Li(4), one V(2), and one V(4) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one V(1) 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 bent 150 degrees geometry to one Li(2) and one V(1) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one Li(1) and one V(2) atom. In the eighth O site, O(8) is bonded in a trigonal planar geometry to one Li(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 Li(1), one Li(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 Li(1), one Li(2), and one V(6) atom. In the twelfth O site, O(12) is bonded to one Li(4), two equivalent Li(3), and one V(4) atom to form distorted corner-sharing OLi3V tetrahedra. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to two equivalent Li(3) and one V(5) atom. In the fourteenth O site, O(14) is bonded to one V(2), one V(4), and two equivalent V(6) atoms to form distorted corner-sharing OV4 trigonal pyramids. In the fifteenth O site, O(15) is bonded in a 4-coordinate geometry to one V(1), 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 Li(3) and one V(7) atom. In the seventeenth O site, O(17) is bonded in a distorted trigonal planar geometry to two equivalent Li(3) and one V(8) atom. In the eighteenth O site, O(18) is bonded in a trigonal planar geometry to one Li(1), one V(1), and one V(7) atom. In the nineteenth O site, O(19) is bonded in a trigonal planar geometry to one Li(2), one V(2), and one V(8) atom. In the twentieth O site, O(20) is bonded in a bent 150 degrees geometry to one Li(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 Li(4), one V(6), and one V(9) atom. In the twenty-third O site, O(23) is bonded in a 3-coordinate geometry to one V(5) and two equivalent V(9) atoms. In the twenty-fourth O site, O(24) is bonded in a distorted trigonal non-coplanar geometry to one V(4) and two equivalent V(9) atoms.