Li2V3WO8 is Spinel-derived structured and crystallizes in the monoclinic C2/m space group. Li(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent W(1)O6 octahedra, and corners with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-62°. There are two inequivalent V sites. In the first V site, 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 W(1)O6 octahedra, and edges with four equivalent V(2)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)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent W(1)O6 octahedra. W(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form WO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one V(1), and two equivalent V(2) atoms to form distorted OLiV3 trigonal pyramids that share corners with three equivalent O(3)LiV2W trigonal pyramids, corners with three equivalent O(1)LiV3 trigonal pyramids, and  an edgeedge with one O(3)LiV2W trigonal pyramid. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one W(1) atom. In the third O site, O(3) is bonded to one Li(1), two equivalent V(2), and one W(1) atom to form distorted OLiV2W trigonal pyramids that share corners with three equivalent O(3)LiV2W trigonal pyramids, corners with three equivalent O(1)LiV3 trigonal pyramids, and  an edgeedge with one O(1)LiV3 trigonal pyramid.
Li2V3WO8 is Spinel-derived structured and crystallizes in the monoclinic C2/m space group. Li(1) is bonded to one O(1), one O(3), and two equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent W(1)O6 octahedra, and corners with six equivalent V(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 57-62°. The Li(1)-O(1) bond length is 2.06 Å. The Li(1)-O(3) bond length is 2.07 Å. Both Li(1)-O(2) bond lengths are 2.03 Å. There are two inequivalent V sites. In the first V site, 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 W(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. Both V(1)-O(1) bond lengths are 2.03 Å. All V(1)-O(2) bond lengths are 2.09 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)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, edges with two equivalent V(2)O6 octahedra, and edges with two equivalent W(1)O6 octahedra. Both V(2)-O(1) bond lengths are 2.02 Å. Both V(2)-O(2) bond lengths are 2.06 Å. Both V(2)-O(3) bond lengths are 2.12 Å. W(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form WO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, edges with two equivalent V(1)O6 octahedra, and edges with four equivalent V(2)O6 octahedra. Both W(1)-O(3) bond lengths are 1.97 Å. All W(1)-O(2) bond lengths are 2.05 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), one V(1), and two equivalent V(2) atoms to form distorted OLiV3 trigonal pyramids that share corners with three equivalent O(3)LiV2W trigonal pyramids, corners with three equivalent O(1)LiV3 trigonal pyramids, and  an edgeedge with one O(3)LiV2W trigonal pyramid. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one V(1), one V(2), and one W(1) atom. In the third O site, O(3) is bonded to one Li(1), two equivalent V(2), and one W(1) atom to form distorted OLiV2W trigonal pyramids that share corners with three equivalent O(3)LiV2W trigonal pyramids, corners with three equivalent O(1)LiV3 trigonal pyramids, and  an edgeedge with one O(1)LiV3 trigonal pyramid.