Li3V5Cr2O12 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) 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 LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent V(3)O6 octahedra, and edges with three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-12°. There are four inequivalent V sites. In the first V site, V(1) 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(2)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. In the second V site, V(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent V(4)O6 octahedra, and edges with three equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-14°. In the fourth V site, V(4) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and edges with three equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-11°. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form CrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-15°. In the second Cr site, Cr(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form CrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and edges with three equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(1), one V(3), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(1)Li2V2Cr square pyramid, corners with two equivalent O(4)Li2V2Cr square pyramids, corners with two equivalent O(5)Li2V2Cr square pyramids, corners with two equivalent O(3)LiV3Cr square pyramids, corners with two equivalent O(6)LiV3Cr square pyramids,  an edgeedge with one O(1)Li2V2Cr square pyramid,  an edgeedge with one O(2)LiV3Cr square pyramid, edges with three equivalent O(4)Li2V2Cr square pyramids, and edges with three equivalent O(5)Li2V2Cr square pyramids. In the second O site, O(2) is bonded to one Li(1), one V(1), one V(2), one V(4), and one Cr(2) atom to form OLiV3Cr square pyramids that share  a cornercorner with one O(2)LiV3Cr square pyramid, corners with two equivalent O(4)Li2V2Cr square pyramids, corners with two equivalent O(5)Li2V2Cr square pyramids, corners with two equivalent O(3)LiV3Cr square pyramids, corners with two equivalent O(6)LiV3Cr square pyramids,  an edgeedge with one O(1)Li2V2Cr square pyramid,  an edgeedge with one O(2)LiV3Cr square pyramid, edges with three equivalent O(3)LiV3Cr square pyramids, and edges with three equivalent O(6)LiV3Cr square pyramids. In the third O site, O(3) is bonded to one Li(1), one V(1), one V(2), one V(4), and one Cr(2) atom to form OLiV3Cr square pyramids that share  a cornercorner with one O(3)LiV3Cr square pyramid, corners with two equivalent O(1)Li2V2Cr square pyramids, corners with two equivalent O(5)Li2V2Cr square pyramids, corners with two equivalent O(2)LiV3Cr square pyramids, corners with two equivalent O(6)LiV3Cr square pyramids,  an edgeedge with one O(4)Li2V2Cr square pyramid,  an edgeedge with one O(3)LiV3Cr square pyramid, edges with three equivalent O(2)LiV3Cr square pyramids, and edges with three equivalent O(6)LiV3Cr square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one V(1), one V(3), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(4)Li2V2Cr square pyramid, corners with two equivalent O(1)Li2V2Cr square pyramids, corners with two equivalent O(5)Li2V2Cr square pyramids, corners with two equivalent O(2)LiV3Cr square pyramids, corners with two equivalent O(6)LiV3Cr square pyramids,  an edgeedge with one O(4)Li2V2Cr square pyramid,  an edgeedge with one O(3)LiV3Cr square pyramid, edges with three equivalent O(1)Li2V2Cr square pyramids, and edges with three equivalent O(5)Li2V2Cr square pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one V(1), one V(3), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(5)Li2V2Cr square pyramid, corners with two equivalent O(1)Li2V2Cr square pyramids, corners with two equivalent O(4)Li2V2Cr square pyramids, corners with two equivalent O(2)LiV3Cr square pyramids, corners with two equivalent O(3)LiV3Cr square pyramids,  an edgeedge with one O(5)Li2V2Cr square pyramid,  an edgeedge with one O(6)LiV3Cr square pyramid, edges with three equivalent O(1)Li2V2Cr square pyramids, and edges with three equivalent O(4)Li2V2Cr square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one V(1), one V(2), one V(4), and one Cr(2) atom to form OLiV3Cr square pyramids that share  a cornercorner with one O(6)LiV3Cr square pyramid, corners with two equivalent O(1)Li2V2Cr square pyramids, corners with two equivalent O(4)Li2V2Cr square pyramids, corners with two equivalent O(2)LiV3Cr square pyramids, corners with two equivalent O(3)LiV3Cr square pyramids,  an edgeedge with one O(5)Li2V2Cr square pyramid,  an edgeedge with one O(6)LiV3Cr square pyramid, edges with three equivalent O(2)LiV3Cr square pyramids, and edges with three equivalent O(3)LiV3Cr square pyramids.
Li3V5Cr2O12 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) 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 LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-14°. The Li(1)-O(1) bond length is 1.98 Å. The Li(1)-O(2) bond length is 2.35 Å. The Li(1)-O(3) bond length is 2.22 Å. The Li(1)-O(4) bond length is 2.03 Å. The Li(1)-O(5) bond length is 2.18 Å. The Li(1)-O(6) bond length is 2.26 Å. In the second Li site, Li(2) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent V(3)O6 octahedra, and edges with three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-12°. Both Li(2)-O(1) bond lengths are 2.19 Å. Both Li(2)-O(4) bond lengths are 2.28 Å. Both Li(2)-O(5) bond lengths are 1.99 Å. There are four inequivalent V sites. In the first V site, V(1) 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(2)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra,  a cornercorner with one V(4)O6 octahedra,  a cornercorner with one Cr(1)O6 octahedra,  a cornercorner with one Cr(2)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one V(2)O6 octahedra,  an edgeedge with one V(3)O6 octahedra,  an edgeedge with one V(4)O6 octahedra,  an edgeedge with one Cr(1)O6 octahedra,  an edgeedge with one Cr(2)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-15°. The V(1)-O(1) bond length is 2.04 Å. The V(1)-O(2) bond length is 2.15 Å. The V(1)-O(3) bond length is 2.24 Å. The V(1)-O(4) bond length is 1.97 Å. The V(1)-O(5) bond length is 1.97 Å. The V(1)-O(6) bond length is 2.23 Å. In the second V site, V(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent V(4)O6 octahedra, and edges with three equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 9-13°. Both V(2)-O(2) bond lengths are 2.05 Å. Both V(2)-O(3) bond lengths are 2.03 Å. Both V(2)-O(6) bond lengths are 2.09 Å. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 3-14°. Both V(3)-O(1) bond lengths are 2.07 Å. Both V(3)-O(4) bond lengths are 2.00 Å. Both V(3)-O(5) bond lengths are 2.10 Å. In the fourth V site, V(4) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form VO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and edges with three equivalent Cr(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-11°. Both V(4)-O(2) bond lengths are 2.08 Å. Both V(4)-O(3) bond lengths are 2.14 Å. Both V(4)-O(6) bond lengths are 1.98 Å. There are two inequivalent Cr sites. In the first Cr site, Cr(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form CrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and edges with three equivalent V(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 4-15°. Both Cr(1)-O(1) bond lengths are 1.98 Å. Both Cr(1)-O(4) bond lengths are 2.09 Å. Both Cr(1)-O(5) bond lengths are 2.05 Å. In the second Cr site, Cr(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(6) atoms to form CrO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with two equivalent V(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with three equivalent V(2)O6 octahedra, and edges with three equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 8-12°. Both Cr(2)-O(2) bond lengths are 2.09 Å. Both Cr(2)-O(3) bond lengths are 1.99 Å. Both Cr(2)-O(6) bond lengths are 2.03 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one Li(2), one V(1), one V(3), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(1)Li2V2Cr square pyramid, corners with two equivalent O(4)Li2V2Cr square pyramids, corners with two equivalent O(5)Li2V2Cr square pyramids, corners with two equivalent O(3)LiV3Cr square pyramids, corners with two equivalent O(6)LiV3Cr square pyramids,  an edgeedge with one O(1)Li2V2Cr square pyramid,  an edgeedge with one O(2)LiV3Cr square pyramid, edges with three equivalent O(4)Li2V2Cr square pyramids, and edges with three equivalent O(5)Li2V2Cr square pyramids. In the second O site, O(2) is bonded to one Li(1), one V(1), one V(2), one V(4), and one Cr(2) atom to form OLiV3Cr square pyramids that share  a cornercorner with one O(2)LiV3Cr square pyramid, corners with two equivalent O(4)Li2V2Cr square pyramids, corners with two equivalent O(5)Li2V2Cr square pyramids, corners with two equivalent O(3)LiV3Cr square pyramids, corners with two equivalent O(6)LiV3Cr square pyramids,  an edgeedge with one O(1)Li2V2Cr square pyramid,  an edgeedge with one O(2)LiV3Cr square pyramid, edges with three equivalent O(3)LiV3Cr square pyramids, and edges with three equivalent O(6)LiV3Cr square pyramids. In the third O site, O(3) is bonded to one Li(1), one V(1), one V(2), one V(4), and one Cr(2) atom to form OLiV3Cr square pyramids that share  a cornercorner with one O(3)LiV3Cr square pyramid, corners with two equivalent O(1)Li2V2Cr square pyramids, corners with two equivalent O(5)Li2V2Cr square pyramids, corners with two equivalent O(2)LiV3Cr square pyramids, corners with two equivalent O(6)LiV3Cr square pyramids,  an edgeedge with one O(4)Li2V2Cr square pyramid,  an edgeedge with one O(3)LiV3Cr square pyramid, edges with three equivalent O(2)LiV3Cr square pyramids, and edges with three equivalent O(6)LiV3Cr square pyramids. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one V(1), one V(3), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(4)Li2V2Cr square pyramid, corners with two equivalent O(1)Li2V2Cr square pyramids, corners with two equivalent O(5)Li2V2Cr square pyramids, corners with two equivalent O(2)LiV3Cr square pyramids, corners with two equivalent O(6)LiV3Cr square pyramids,  an edgeedge with one O(4)Li2V2Cr square pyramid,  an edgeedge with one O(3)LiV3Cr square pyramid, edges with three equivalent O(1)Li2V2Cr square pyramids, and edges with three equivalent O(5)Li2V2Cr square pyramids. In the fifth O site, O(5) is bonded to one Li(1), one Li(2), one V(1), one V(3), and one Cr(1) atom to form OLi2V2Cr square pyramids that share  a cornercorner with one O(5)Li2V2Cr square pyramid, corners with two equivalent O(1)Li2V2Cr square pyramids, corners with two equivalent O(4)Li2V2Cr square pyramids, corners with two equivalent O(2)LiV3Cr square pyramids, corners with two equivalent O(3)LiV3Cr square pyramids,  an edgeedge with one O(5)Li2V2Cr square pyramid,  an edgeedge with one O(6)LiV3Cr square pyramid, edges with three equivalent O(1)Li2V2Cr square pyramids, and edges with three equivalent O(4)Li2V2Cr square pyramids. In the sixth O site, O(6) is bonded to one Li(1), one V(1), one V(2), one V(4), and one Cr(2) atom to form OLiV3Cr square pyramids that share  a cornercorner with one O(6)LiV3Cr square pyramid, corners with two equivalent O(1)Li2V2Cr square pyramids, corners with two equivalent O(4)Li2V2Cr square pyramids, corners with two equivalent O(2)LiV3Cr square pyramids, corners with two equivalent O(3)LiV3Cr square pyramids,  an edgeedge with one O(5)Li2V2Cr square pyramid,  an edgeedge with one O(6)LiV3Cr square pyramid, edges with three equivalent O(2)LiV3Cr square pyramids, and edges with three equivalent O(3)LiV3Cr square pyramids.