Li6V5O12 crystallizes in the monoclinic C2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with three equivalent Li(4)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-15°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-16°. In the fourth Li site, Li(4) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-16°. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-15°. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-13°. In the third V site, V(3) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. In the fourth V site, V(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one V(1), one V(2), and one V(4) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(3)Li4V2 octahedra,  a cornercorner with one O(4)Li4V2 octahedra,  a cornercorner with one O(6)Li4V2 octahedra, corners with three equivalent O(2)Li2V3 square pyramids, corners with three equivalent O(5)Li2V3 square pyramids,  an edgeedge with one O(3)Li4V2 octahedra,  an edgeedge with one O(4)Li4V2 octahedra,  an edgeedge with one O(6)Li4V2 octahedra,  an edgeedge with one O(1)Li2V3 square pyramid, edges with two equivalent O(2)Li2V3 square pyramids, and edges with two equivalent O(5)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 5-14°. In the second O site, O(2) is bonded to one Li(2), one Li(3), one V(1), one V(2), and one V(4) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(3)Li4V2 octahedra,  a cornercorner with one O(4)Li4V2 octahedra,  a cornercorner with one O(6)Li4V2 octahedra,  a cornercorner with one O(5)Li2V3 square pyramid, corners with two equivalent O(2)Li2V3 square pyramids, corners with three equivalent O(1)Li2V3 square pyramids,  an edgeedge with one O(3)Li4V2 octahedra,  an edgeedge with one O(4)Li4V2 octahedra,  an edgeedge with one O(6)Li4V2 octahedra, edges with two equivalent O(1)Li2V3 square pyramids, and edges with three equivalent O(5)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 2-21°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(3), and one V(4) atom to form OLi4V2 octahedra that share  a cornercorner with one O(3)Li4V2 octahedra,  a cornercorner with one O(4)Li4V2 octahedra,  a cornercorner with one O(6)Li4V2 octahedra,  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(2)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid,  an edgeedge with one O(3)Li4V2 octahedra, edges with four equivalent O(4)Li4V2 octahedra, edges with four equivalent O(6)Li4V2 octahedra,  an edgeedge with one O(1)Li2V3 square pyramid,  an edgeedge with one O(2)Li2V3 square pyramid, and  an edgeedge with one O(5)Li2V3 square pyramid. The corner-sharing octahedral tilt angles range from 5-7°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(3), and one V(4) atom to form OLi4V2 octahedra that share  a cornercorner with one O(3)Li4V2 octahedra,  a cornercorner with one O(4)Li4V2 octahedra,  a cornercorner with one O(6)Li4V2 octahedra,  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(2)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid,  an edgeedge with one O(4)Li4V2 octahedra, edges with four equivalent O(3)Li4V2 octahedra, edges with four equivalent O(6)Li4V2 octahedra,  an edgeedge with one O(1)Li2V3 square pyramid,  an edgeedge with one O(2)Li2V3 square pyramid, and  an edgeedge with one O(5)Li2V3 square pyramid. The corner-sharing octahedral tilt angles range from 6-13°. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one V(1), one V(2), and one V(4) atom to form distorted OLi2V3 square pyramids that share  a cornercorner with one O(3)Li4V2 octahedra,  a cornercorner with one O(4)Li4V2 octahedra,  a cornercorner with one O(6)Li4V2 octahedra,  a cornercorner with one O(2)Li2V3 square pyramid, corners with two equivalent O(5)Li2V3 square pyramids, corners with three equivalent O(1)Li2V3 square pyramids,  an edgeedge with one O(3)Li4V2 octahedra,  an edgeedge with one O(4)Li4V2 octahedra,  an edgeedge with one O(6)Li4V2 octahedra, edges with two equivalent O(1)Li2V3 square pyramids, and edges with three equivalent O(2)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 1-14°. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(3), and one V(4) atom to form distorted OLi4V2 octahedra that share  a cornercorner with one O(3)Li4V2 octahedra,  a cornercorner with one O(4)Li4V2 octahedra,  a cornercorner with one O(6)Li4V2 octahedra,  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(2)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid,  an edgeedge with one O(6)Li4V2 octahedra, edges with four equivalent O(3)Li4V2 octahedra, edges with four equivalent O(4)Li4V2 octahedra,  an edgeedge with one O(1)Li2V3 square pyramid,  an edgeedge with one O(2)Li2V3 square pyramid, and  an edgeedge with one O(5)Li2V3 square pyramid. The corner-sharing octahedral tilt angles range from 3-13°.
Li6V5O12 crystallizes in the monoclinic C2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with three equivalent Li(4)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-15°. Both Li(1)-O(3) bond lengths are 2.02 Å. Both Li(1)-O(4) bond lengths are 2.03 Å. Both Li(1)-O(6) bond lengths are 2.36 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with three equivalent Li(3)O6 octahedra, and edges with three equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. The Li(2)-O(1) bond length is 2.01 Å. The Li(2)-O(2) bond length is 2.45 Å. The Li(2)-O(3) bond length is 2.19 Å. The Li(2)-O(4) bond length is 2.06 Å. The Li(2)-O(5) bond length is 2.08 Å. The Li(2)-O(6) bond length is 2.07 Å. In the third Li site, Li(3) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form distorted LiO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-16°. The Li(3)-O(1) bond length is 2.11 Å. The Li(3)-O(2) bond length is 1.98 Å. The Li(3)-O(3) bond length is 2.10 Å. The Li(3)-O(4) bond length is 2.31 Å. The Li(3)-O(5) bond length is 2.56 Å. The Li(3)-O(6) bond length is 1.97 Å. In the fourth Li site, Li(4) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-16°. Both Li(4)-O(3) bond lengths are 2.13 Å. Both Li(4)-O(4) bond lengths are 2.10 Å. Both Li(4)-O(6) bond lengths are 2.09 Å. There are four inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with three equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 6-15°. Both V(1)-O(1) bond lengths are 2.05 Å. Both V(1)-O(2) bond lengths are 2.03 Å. Both V(1)-O(5) bond lengths are 2.04 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-13°. Both V(2)-O(1) bond lengths are 2.01 Å. Both V(2)-O(2) bond lengths are 2.04 Å. Both V(2)-O(5) bond lengths are 2.08 Å. In the third V site, V(3) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Li(3)O6 octahedra, corners with two equivalent V(4)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, edges with two equivalent V(4)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-11°. Both V(3)-O(3) bond lengths are 2.06 Å. Both V(3)-O(4) bond lengths are 1.92 Å. Both V(3)-O(6) bond lengths are 1.99 Å. In the fourth V site, V(4) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(6) atom to form VO6 octahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  an edgeedge with one Li(1)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one V(1)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. The V(4)-O(1) bond length is 2.02 Å. The V(4)-O(2) bond length is 1.95 Å. The V(4)-O(3) bond length is 1.94 Å. The V(4)-O(4) bond length is 2.06 Å. The V(4)-O(5) bond length is 1.91 Å. The V(4)-O(6) bond length is 1.98 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), one Li(3), one V(1), one V(2), and one V(4) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(3)Li4V2 octahedra,  a cornercorner with one O(4)Li4V2 octahedra,  a cornercorner with one O(6)Li4V2 octahedra, corners with three equivalent O(2)Li2V3 square pyramids, corners with three equivalent O(5)Li2V3 square pyramids,  an edgeedge with one O(3)Li4V2 octahedra,  an edgeedge with one O(4)Li4V2 octahedra,  an edgeedge with one O(6)Li4V2 octahedra,  an edgeedge with one O(1)Li2V3 square pyramid, edges with two equivalent O(2)Li2V3 square pyramids, and edges with two equivalent O(5)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 5-14°. In the second O site, O(2) is bonded to one Li(2), one Li(3), one V(1), one V(2), and one V(4) atom to form OLi2V3 square pyramids that share  a cornercorner with one O(3)Li4V2 octahedra,  a cornercorner with one O(4)Li4V2 octahedra,  a cornercorner with one O(6)Li4V2 octahedra,  a cornercorner with one O(5)Li2V3 square pyramid, corners with two equivalent O(2)Li2V3 square pyramids, corners with three equivalent O(1)Li2V3 square pyramids,  an edgeedge with one O(3)Li4V2 octahedra,  an edgeedge with one O(4)Li4V2 octahedra,  an edgeedge with one O(6)Li4V2 octahedra, edges with two equivalent O(1)Li2V3 square pyramids, and edges with three equivalent O(5)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 2-21°. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(3), and one V(4) atom to form OLi4V2 octahedra that share  a cornercorner with one O(3)Li4V2 octahedra,  a cornercorner with one O(4)Li4V2 octahedra,  a cornercorner with one O(6)Li4V2 octahedra,  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(2)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid,  an edgeedge with one O(3)Li4V2 octahedra, edges with four equivalent O(4)Li4V2 octahedra, edges with four equivalent O(6)Li4V2 octahedra,  an edgeedge with one O(1)Li2V3 square pyramid,  an edgeedge with one O(2)Li2V3 square pyramid, and  an edgeedge with one O(5)Li2V3 square pyramid. The corner-sharing octahedral tilt angles range from 5-7°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(3), and one V(4) atom to form OLi4V2 octahedra that share  a cornercorner with one O(3)Li4V2 octahedra,  a cornercorner with one O(4)Li4V2 octahedra,  a cornercorner with one O(6)Li4V2 octahedra,  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(2)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid,  an edgeedge with one O(4)Li4V2 octahedra, edges with four equivalent O(3)Li4V2 octahedra, edges with four equivalent O(6)Li4V2 octahedra,  an edgeedge with one O(1)Li2V3 square pyramid,  an edgeedge with one O(2)Li2V3 square pyramid, and  an edgeedge with one O(5)Li2V3 square pyramid. The corner-sharing octahedral tilt angles range from 6-13°. In the fifth O site, O(5) is bonded to one Li(2), one Li(3), one V(1), one V(2), and one V(4) atom to form distorted OLi2V3 square pyramids that share  a cornercorner with one O(3)Li4V2 octahedra,  a cornercorner with one O(4)Li4V2 octahedra,  a cornercorner with one O(6)Li4V2 octahedra,  a cornercorner with one O(2)Li2V3 square pyramid, corners with two equivalent O(5)Li2V3 square pyramids, corners with three equivalent O(1)Li2V3 square pyramids,  an edgeedge with one O(3)Li4V2 octahedra,  an edgeedge with one O(4)Li4V2 octahedra,  an edgeedge with one O(6)Li4V2 octahedra, edges with two equivalent O(1)Li2V3 square pyramids, and edges with three equivalent O(2)Li2V3 square pyramids. The corner-sharing octahedral tilt angles range from 1-14°. In the sixth O site, O(6) is bonded to one Li(1), one Li(2), one Li(3), one Li(4), one V(3), and one V(4) atom to form distorted OLi4V2 octahedra that share  a cornercorner with one O(3)Li4V2 octahedra,  a cornercorner with one O(4)Li4V2 octahedra,  a cornercorner with one O(6)Li4V2 octahedra,  a cornercorner with one O(1)Li2V3 square pyramid,  a cornercorner with one O(2)Li2V3 square pyramid,  a cornercorner with one O(5)Li2V3 square pyramid,  an edgeedge with one O(6)Li4V2 octahedra, edges with four equivalent O(3)Li4V2 octahedra, edges with four equivalent O(4)Li4V2 octahedra,  an edgeedge with one O(1)Li2V3 square pyramid,  an edgeedge with one O(2)Li2V3 square pyramid, and  an edgeedge with one O(5)Li2V3 square pyramid. The corner-sharing octahedral tilt angles range from 3-13°.