Li2V3WO8 is Spinel-derived structured and crystallizes in the hexagonal P6_3mc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent W(1)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-61°. In the second Li site, Li(2) is bonded to one O(4) and three equivalent O(1) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent W(1)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-62°. V(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent W(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one W(1)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. W(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form WO6 octahedra that share corners with six equivalent V(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. 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(2), two equivalent V(1), and one W(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent V(1), and one W(1) atom. In the third O site, O(3) is bonded to one Li(1) and three equivalent V(1) atoms to form distorted corner-sharing OLiV3 trigonal pyramids. In the fourth O site, O(4) is bonded to one Li(2) and three equivalent V(1) atoms to form corner-sharing OLiV3 tetrahedra.
Li2V3WO8 is Spinel-derived structured and crystallizes in the hexagonal P6_3mc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(3) and three equivalent O(2) atoms to form LiO4 tetrahedra that share corners with three equivalent W(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(3) bond length is 2.02 Å. All Li(1)-O(2) bond lengths are 2.01 Å. In the second Li site, Li(2) is bonded to one O(4) and three equivalent O(1) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent V(1)O6 octahedra, corners with three equivalent W(1)O6 octahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 61-62°. The Li(2)-O(4) bond length is 1.81 Å. All Li(2)-O(1) bond lengths are 2.04 Å. V(1) is bonded to one O(3), one O(4), two equivalent O(1), and two equivalent O(2) atoms to form VO6 octahedra that share corners with two equivalent W(1)O6 octahedra,  a cornercorner with one Li(2)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one W(1)O6 octahedra, edges with four equivalent V(1)O6 octahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. The V(1)-O(3) bond length is 1.99 Å. The V(1)-O(4) bond length is 2.00 Å. Both V(1)-O(1) bond lengths are 2.14 Å. Both V(1)-O(2) bond lengths are 2.06 Å. W(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form WO6 octahedra that share corners with six equivalent V(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles are 49°. All W(1)-O(1) bond lengths are 1.98 Å. All W(1)-O(2) bond lengths are 2.07 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(2), two equivalent V(1), and one W(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent V(1), and one W(1) atom. In the third O site, O(3) is bonded to one Li(1) and three equivalent V(1) atoms to form distorted corner-sharing OLiV3 trigonal pyramids. In the fourth O site, O(4) is bonded to one Li(2) and three equivalent V(1) atoms to form corner-sharing OLiV3 tetrahedra.