Li2V3SnO8 is Spinel-derived structured and crystallizes in the trigonal R3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-62°. In the second Li site, Li(2) is bonded to three equivalent O(2) and three equivalent O(3) atoms to form LiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Sn(1)O4 tetrahedra, and edges with six equivalent V(1)O6 octahedra. V(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Sn(1)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. Sn(1) is bonded to one O(4) and three equivalent O(3) atoms to form SnO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 60°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1) and three equivalent V(1) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent V(1) atoms. In the third O site, O(3) is bonded to one Li(2), two equivalent V(1), and one Sn(1) atom to form distorted OLiV2Sn tetrahedra that share  a cornercorner with one O(4)V3Sn tetrahedra, corners with two equivalent O(3)LiV2Sn tetrahedra,  an edgeedge with one O(4)V3Sn tetrahedra, and edges with two equivalent O(3)LiV2Sn tetrahedra. In the fourth O site, O(4) is bonded to three equivalent V(1) and one Sn(1) atom to form a mixture of distorted edge and corner-sharing OV3Sn tetrahedra.
Li2V3SnO8 is Spinel-derived structured and crystallizes in the trigonal R3m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 54-62°. The Li(1)-O(1) bond length is 2.03 Å. All Li(1)-O(2) bond lengths are 2.01 Å. In the second Li site, Li(2) is bonded to three equivalent O(2) and three equivalent O(3) atoms to form LiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Sn(1)O4 tetrahedra, and edges with six equivalent V(1)O6 octahedra. All Li(2)-O(2) bond lengths are 2.13 Å. All Li(2)-O(3) bond lengths are 2.11 Å. V(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form VO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Sn(1)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The V(1)-O(1) bond length is 2.02 Å. The V(1)-O(4) bond length is 2.14 Å. Both V(1)-O(2) bond lengths are 1.92 Å. Both V(1)-O(3) bond lengths are 2.09 Å. Sn(1) is bonded to one O(4) and three equivalent O(3) atoms to form SnO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 60°. The Sn(1)-O(4) bond length is 2.03 Å. All Sn(1)-O(3) bond lengths are 2.00 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a rectangular see-saw-like geometry to one Li(1) and three equivalent V(1) atoms. In the second O site, O(2) is bonded in a rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent V(1) atoms. In the third O site, O(3) is bonded to one Li(2), two equivalent V(1), and one Sn(1) atom to form distorted OLiV2Sn tetrahedra that share  a cornercorner with one O(4)V3Sn tetrahedra, corners with two equivalent O(3)LiV2Sn tetrahedra,  an edgeedge with one O(4)V3Sn tetrahedra, and edges with two equivalent O(3)LiV2Sn tetrahedra. In the fourth O site, O(4) is bonded to three equivalent V(1) and one Sn(1) atom to form a mixture of distorted edge and corner-sharing OV3Sn tetrahedra.