Li2V3SnO8 is Spinel-derived structured and crystallizes in the trigonal R-3m space group. Li(1) is bonded to one O(1) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Sn(1)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-61°. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Sn(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. Sn(1) is bonded to six equivalent O(2) atoms to form SnO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra and edges with six equivalent V(1)O6 octahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1) and three equivalent V(1) atoms to form distorted OLiV3 tetrahedra that share corners with three equivalent O(1)LiV3 tetrahedra, corners with nine equivalent O(2)LiV2Sn trigonal pyramids, and edges with three equivalent O(2)LiV2Sn trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), two equivalent V(1), and one Sn(1) atom to form distorted OLiV2Sn trigonal pyramids that share corners with three equivalent O(1)LiV3 tetrahedra, corners with nine equivalent O(2)LiV2Sn trigonal pyramids,  an edgeedge with one O(1)LiV3 tetrahedra, and edges with two equivalent O(2)LiV2Sn trigonal pyramids.
Li2V3SnO8 is Spinel-derived structured and crystallizes in the trigonal R-3m space group. Li(1) is bonded to one O(1) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Sn(1)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-61°. The Li(1)-O(1) bond length is 2.22 Å. All Li(1)-O(2) bond lengths are 2.01 Å. V(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form VO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent Sn(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. Both V(1)-O(1) bond lengths are 2.00 Å. All V(1)-O(2) bond lengths are 2.05 Å. Sn(1) is bonded to six equivalent O(2) atoms to form SnO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra and edges with six equivalent V(1)O6 octahedra. All Sn(1)-O(2) bond lengths are 2.10 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1) and three equivalent V(1) atoms to form distorted OLiV3 tetrahedra that share corners with three equivalent O(1)LiV3 tetrahedra, corners with nine equivalent O(2)LiV2Sn trigonal pyramids, and edges with three equivalent O(2)LiV2Sn trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), two equivalent V(1), and one Sn(1) atom to form distorted OLiV2Sn trigonal pyramids that share corners with three equivalent O(1)LiV3 tetrahedra, corners with nine equivalent O(2)LiV2Sn trigonal pyramids,  an edgeedge with one O(1)LiV3 tetrahedra, and edges with two equivalent O(2)LiV2Sn trigonal pyramids.