Li4V3O8 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share corners with six equivalent Li(2)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. The corner-sharing octahedral tilt angles are 13°. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six 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. The corner-sharing octahedral tilt angles are 13°. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. There are three 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 Li(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)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 edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. 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 Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one V(1), one V(2), and one V(3) atom to form distorted OLiV3 trigonal pyramids that share corners with three equivalent O(2)Li3V2 square pyramids, corners with three equivalent O(3)Li3V2 square pyramids, corners with three equivalent O(4)Li3V2 square pyramids, corners with three equivalent O(1)LiV3 trigonal pyramids,  an edgeedge with one O(2)Li3V2 square pyramid,  an edgeedge with one O(3)Li3V2 square pyramid, and  an edgeedge with one O(4)Li3V2 square pyramid. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one V(1), and one V(2) atom to form OLi3V2 square pyramids that share  a cornercorner with one O(3)Li3V2 square pyramid,  a cornercorner with one O(4)Li3V2 square pyramid, corners with four equivalent O(2)Li3V2 square pyramids, corners with three equivalent O(1)LiV3 trigonal pyramids, edges with three equivalent O(3)Li3V2 square pyramids, edges with three equivalent O(4)Li3V2 square pyramids, and  an edgeedge with one O(1)LiV3 trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(2), and one V(3) atom to form OLi3V2 square pyramids that share  a cornercorner with one O(2)Li3V2 square pyramid,  a cornercorner with one O(4)Li3V2 square pyramid, corners with four equivalent O(3)Li3V2 square pyramids, corners with three equivalent O(1)LiV3 trigonal pyramids, edges with three equivalent O(2)Li3V2 square pyramids, edges with three equivalent O(4)Li3V2 square pyramids, and  an edgeedge with one O(1)LiV3 trigonal pyramid. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one V(1), and one V(3) atom to form OLi3V2 square pyramids that share  a cornercorner with one O(2)Li3V2 square pyramid,  a cornercorner with one O(3)Li3V2 square pyramid, corners with four equivalent O(4)Li3V2 square pyramids, corners with three equivalent O(1)LiV3 trigonal pyramids, edges with three equivalent O(2)Li3V2 square pyramids, edges with three equivalent O(3)Li3V2 square pyramids, and  an edgeedge with one O(1)LiV3 trigonal pyramid.
Li4V3O8 crystallizes in the triclinic P-1 space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share corners with six equivalent Li(2)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. The corner-sharing octahedral tilt angles are 13°. Both Li(1)-O(2) bond lengths are 2.20 Å. Both Li(1)-O(3) bond lengths are 2.20 Å. Both Li(1)-O(4) bond lengths are 2.21 Å. In the second Li site, Li(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with six 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. The corner-sharing octahedral tilt angles are 13°. Both Li(2)-O(2) bond lengths are 2.07 Å. Both Li(2)-O(3) bond lengths are 2.07 Å. Both Li(2)-O(4) bond lengths are 2.07 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(2), one O(3), and one O(4) atom. The Li(3)-O(1) bond length is 1.88 Å. The Li(3)-O(2) bond length is 2.10 Å. The Li(3)-O(3) bond length is 2.11 Å. The Li(3)-O(4) bond length is 2.11 Å. There are three 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 Li(2)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. Both V(1)-O(1) bond lengths are 2.00 Å. Both V(1)-O(2) bond lengths are 1.90 Å. Both V(1)-O(4) bond lengths are 2.02 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 edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(3)O6 octahedra. Both V(2)-O(1) bond lengths are 2.00 Å. Both V(2)-O(2) bond lengths are 2.02 Å. Both V(2)-O(3) bond lengths are 1.90 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 Li(2)O6 octahedra, edges with two equivalent V(1)O6 octahedra, and edges with two equivalent V(2)O6 octahedra. Both V(3)-O(1) bond lengths are 2.00 Å. Both V(3)-O(3) bond lengths are 2.02 Å. Both V(3)-O(4) bond lengths are 1.90 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), one V(1), one V(2), and one V(3) atom to form distorted OLiV3 trigonal pyramids that share corners with three equivalent O(2)Li3V2 square pyramids, corners with three equivalent O(3)Li3V2 square pyramids, corners with three equivalent O(4)Li3V2 square pyramids, corners with three equivalent O(1)LiV3 trigonal pyramids,  an edgeedge with one O(2)Li3V2 square pyramid,  an edgeedge with one O(3)Li3V2 square pyramid, and  an edgeedge with one O(4)Li3V2 square pyramid. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Li(3), one V(1), and one V(2) atom to form OLi3V2 square pyramids that share  a cornercorner with one O(3)Li3V2 square pyramid,  a cornercorner with one O(4)Li3V2 square pyramid, corners with four equivalent O(2)Li3V2 square pyramids, corners with three equivalent O(1)LiV3 trigonal pyramids, edges with three equivalent O(3)Li3V2 square pyramids, edges with three equivalent O(4)Li3V2 square pyramids, and  an edgeedge with one O(1)LiV3 trigonal pyramid. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Li(3), one V(2), and one V(3) atom to form OLi3V2 square pyramids that share  a cornercorner with one O(2)Li3V2 square pyramid,  a cornercorner with one O(4)Li3V2 square pyramid, corners with four equivalent O(3)Li3V2 square pyramids, corners with three equivalent O(1)LiV3 trigonal pyramids, edges with three equivalent O(2)Li3V2 square pyramids, edges with three equivalent O(4)Li3V2 square pyramids, and  an edgeedge with one O(1)LiV3 trigonal pyramid. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), one Li(3), one V(1), and one V(3) atom to form OLi3V2 square pyramids that share  a cornercorner with one O(2)Li3V2 square pyramid,  a cornercorner with one O(3)Li3V2 square pyramid, corners with four equivalent O(4)Li3V2 square pyramids, corners with three equivalent O(1)LiV3 trigonal pyramids, edges with three equivalent O(2)Li3V2 square pyramids, edges with three equivalent O(3)Li3V2 square pyramids, and  an edgeedge with one O(1)LiV3 trigonal pyramid.