Li4V5SnO12 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a distorted see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form edge-sharing VO6 octahedra. In the second V site, V(2) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form VO6 octahedra that share edges with three equivalent V(2)O6 octahedra and edges with three equivalent Sn(1)O6 octahedra. In the third V site, V(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form edge-sharing VO6 octahedra. Sn(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form SnO6 octahedra that share edges with six equivalent V(2)O6 octahedra. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent V(2), and one Sn(1) atom to form distorted OLi2V2Sn trigonal bipyramids that share corners with two equivalent O(2)Li2V3 trigonal bipyramids, corners with three equivalent O(1)Li2V2Sn trigonal bipyramids,  an edgeedge with one O(2)Li2V3 trigonal bipyramid, and edges with four equivalent O(1)Li2V2Sn trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Li(1), one V(3), and two equivalent V(1) atoms to form OLi2V3 trigonal bipyramids that share corners with two equivalent O(1)Li2V2Sn trigonal bipyramids, corners with three equivalent O(2)Li2V3 trigonal bipyramids,  an edgeedge with one O(1)Li2V2Sn trigonal bipyramid, and edges with four equivalent O(2)Li2V3 trigonal bipyramids. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to two equivalent V(2) and one Sn(1) atom.
Li4V5SnO12 crystallizes in the monoclinic C2/m space group. Li(1) is bonded in a distorted see-saw-like geometry to two equivalent O(1) and two equivalent O(2) atoms. There is one shorter (2.02 Å) and one longer (2.16 Å) Li(1)-O(1) bond length. There is one shorter (2.04 Å) and one longer (2.16 Å) Li(1)-O(2) bond length. There are three inequivalent V sites. In the first V site, V(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form edge-sharing VO6 octahedra. Both V(1)-O(3) bond lengths are 1.99 Å. All V(1)-O(2) bond lengths are 2.06 Å. In the second V site, V(2) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form VO6 octahedra that share edges with three equivalent V(2)O6 octahedra and edges with three equivalent Sn(1)O6 octahedra. Both V(2)-O(4) bond lengths are 2.01 Å. There are two shorter (2.03 Å) and two longer (2.12 Å) V(2)-O(1) bond lengths. In the third V site, V(3) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form edge-sharing VO6 octahedra. Both V(3)-O(3) bond lengths are 2.01 Å. All V(3)-O(2) bond lengths are 2.10 Å. Sn(1) is bonded to two equivalent O(4) and four equivalent O(1) atoms to form SnO6 octahedra that share edges with six equivalent V(2)O6 octahedra. Both Sn(1)-O(4) bond lengths are 2.06 Å. All Sn(1)-O(1) bond lengths are 2.13 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), two equivalent V(2), and one Sn(1) atom to form distorted OLi2V2Sn trigonal bipyramids that share corners with two equivalent O(2)Li2V3 trigonal bipyramids, corners with three equivalent O(1)Li2V2Sn trigonal bipyramids,  an edgeedge with one O(2)Li2V3 trigonal bipyramid, and edges with four equivalent O(1)Li2V2Sn trigonal bipyramids. In the second O site, O(2) is bonded to two equivalent Li(1), one V(3), and two equivalent V(1) atoms to form OLi2V3 trigonal bipyramids that share corners with two equivalent O(1)Li2V2Sn trigonal bipyramids, corners with three equivalent O(2)Li2V3 trigonal bipyramids,  an edgeedge with one O(1)Li2V2Sn trigonal bipyramid, and edges with four equivalent O(2)Li2V3 trigonal bipyramids. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one V(3) and two equivalent V(1) atoms. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to two equivalent V(2) and one Sn(1) atom.