LiV4Mn2O8 crystallizes in the triclinic P-1 space group. Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with six equivalent V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. 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(4) atoms to form VO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. In the fourth V site, V(4) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. Mn(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one V(1), one V(2), one V(3), and one Mn(1) atom to form OLiMnV3 square pyramids that share  a cornercorner with one O(2)LiMnV3 square pyramid,  a cornercorner with one O(3)LiMnV3 square pyramid, corners with four equivalent O(1)LiMnV3 square pyramids, corners with three equivalent O(4)MnV3 trigonal pyramids, edges with three equivalent O(2)LiMnV3 square pyramids, edges with three equivalent O(3)LiMnV3 square pyramids, and  an edgeedge with one O(4)MnV3 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one V(1), one V(2), one V(4), and one Mn(1) atom to form OLiMnV3 square pyramids that share  a cornercorner with one O(1)LiMnV3 square pyramid,  a cornercorner with one O(3)LiMnV3 square pyramid, corners with four equivalent O(2)LiMnV3 square pyramids, corners with three equivalent O(4)MnV3 trigonal pyramids, edges with three equivalent O(1)LiMnV3 square pyramids, edges with three equivalent O(3)LiMnV3 square pyramids, and  an edgeedge with one O(4)MnV3 trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one V(2), one V(3), one V(4), and one Mn(1) atom to form OLiMnV3 square pyramids that share  a cornercorner with one O(1)LiMnV3 square pyramid,  a cornercorner with one O(2)LiMnV3 square pyramid, corners with four equivalent O(3)LiMnV3 square pyramids, corners with three equivalent O(4)MnV3 trigonal pyramids, edges with three equivalent O(1)LiMnV3 square pyramids, edges with three equivalent O(2)LiMnV3 square pyramids, and  an edgeedge with one O(4)MnV3 trigonal pyramid. In the fourth O site, O(4) is bonded to one V(1), one V(3), one V(4), and one Mn(1) atom to form distorted OMnV3 trigonal pyramids that share corners with three equivalent O(1)LiMnV3 square pyramids, corners with three equivalent O(2)LiMnV3 square pyramids, corners with three equivalent O(3)LiMnV3 square pyramids, corners with three equivalent O(4)MnV3 trigonal pyramids,  an edgeedge with one O(1)LiMnV3 square pyramid,  an edgeedge with one O(2)LiMnV3 square pyramid, and  an edgeedge with one O(3)LiMnV3 square pyramid.
LiV4Mn2O8 crystallizes in the triclinic P-1 space group. Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with six equivalent V(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. Both Li(1)-O(1) bond lengths are 2.19 Å. Both Li(1)-O(2) bond lengths are 2.15 Å. Both Li(1)-O(3) bond lengths are 2.17 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(4) atoms to form VO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. Both V(1)-O(1) bond lengths are 2.09 Å. Both V(1)-O(2) bond lengths are 2.08 Å. Both V(1)-O(4) bond lengths are 2.03 Å. In the second V site, V(2) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(3)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 7-9°. Both V(2)-O(1) bond lengths are 2.24 Å. Both V(2)-O(2) bond lengths are 2.25 Å. Both V(2)-O(3) bond lengths are 2.24 Å. In the third V site, V(3) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(4)O6 octahedra. Both V(3)-O(1) bond lengths are 2.10 Å. Both V(3)-O(3) bond lengths are 2.09 Å. Both V(3)-O(4) bond lengths are 2.01 Å. In the fourth V site, V(4) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form VO6 octahedra that share edges with two equivalent Li(1)O6 octahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. Both V(4)-O(2) bond lengths are 2.07 Å. Both V(4)-O(3) bond lengths are 2.08 Å. Both V(4)-O(4) bond lengths are 2.05 Å. Mn(1) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Mn(1)-O(1) bond length is 2.12 Å. The Mn(1)-O(2) bond length is 2.15 Å. The Mn(1)-O(3) bond length is 2.14 Å. The Mn(1)-O(4) bond length is 1.99 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one V(1), one V(2), one V(3), and one Mn(1) atom to form OLiMnV3 square pyramids that share  a cornercorner with one O(2)LiMnV3 square pyramid,  a cornercorner with one O(3)LiMnV3 square pyramid, corners with four equivalent O(1)LiMnV3 square pyramids, corners with three equivalent O(4)MnV3 trigonal pyramids, edges with three equivalent O(2)LiMnV3 square pyramids, edges with three equivalent O(3)LiMnV3 square pyramids, and  an edgeedge with one O(4)MnV3 trigonal pyramid. In the second O site, O(2) is bonded to one Li(1), one V(1), one V(2), one V(4), and one Mn(1) atom to form OLiMnV3 square pyramids that share  a cornercorner with one O(1)LiMnV3 square pyramid,  a cornercorner with one O(3)LiMnV3 square pyramid, corners with four equivalent O(2)LiMnV3 square pyramids, corners with three equivalent O(4)MnV3 trigonal pyramids, edges with three equivalent O(1)LiMnV3 square pyramids, edges with three equivalent O(3)LiMnV3 square pyramids, and  an edgeedge with one O(4)MnV3 trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one V(2), one V(3), one V(4), and one Mn(1) atom to form OLiMnV3 square pyramids that share  a cornercorner with one O(1)LiMnV3 square pyramid,  a cornercorner with one O(2)LiMnV3 square pyramid, corners with four equivalent O(3)LiMnV3 square pyramids, corners with three equivalent O(4)MnV3 trigonal pyramids, edges with three equivalent O(1)LiMnV3 square pyramids, edges with three equivalent O(2)LiMnV3 square pyramids, and  an edgeedge with one O(4)MnV3 trigonal pyramid. In the fourth O site, O(4) is bonded to one V(1), one V(3), one V(4), and one Mn(1) atom to form distorted OMnV3 trigonal pyramids that share corners with three equivalent O(1)LiMnV3 square pyramids, corners with three equivalent O(2)LiMnV3 square pyramids, corners with three equivalent O(3)LiMnV3 square pyramids, corners with three equivalent O(4)MnV3 trigonal pyramids,  an edgeedge with one O(1)LiMnV3 square pyramid,  an edgeedge with one O(2)LiMnV3 square pyramid, and  an edgeedge with one O(3)LiMnV3 square pyramid.