Li2V3MnO8 is Spinel-derived structured and crystallizes in the trigonal P31c 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 Mn(1)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-68°. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(4) and three equivalent O(1) atoms. 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 Mn(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-58°. Mn(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent V(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-58°. 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 Mn(1) atom. In the second O site, O(2) is bonded to one Li(1), two equivalent V(1), and one Mn(1) atom to form distorted OLiMnV2 tetrahedra that share corners with two equivalent O(2)LiMnV2 tetrahedra, corners with two equivalent O(4)LiV3 tetrahedra, and edges with two equivalent O(2)LiMnV2 tetrahedra. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1) and three equivalent V(1) atoms. In the fourth O site, O(4) is bonded to one Li(2) and three equivalent V(1) atoms to form distorted corner-sharing OLiV3 tetrahedra.
Li2V3MnO8 is Spinel-derived structured and crystallizes in the trigonal P31c 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 Mn(1)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 56-68°. The Li(1)-O(3) bond length is 2.07 Å. All Li(1)-O(2) bond lengths are 2.01 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to one O(4) and three equivalent O(1) atoms. The Li(2)-O(4) bond length is 1.82 Å. All Li(2)-O(1) bond lengths are 1.95 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 Mn(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-58°. The V(1)-O(3) bond length is 2.02 Å. The V(1)-O(4) bond length is 2.00 Å. There is one shorter (1.95 Å) and one longer (1.99 Å) V(1)-O(1) bond length. There is one shorter (1.85 Å) and one longer (2.08 Å) V(1)-O(2) bond length. Mn(1) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form MnO6 octahedra that share corners with six equivalent V(1)O6 octahedra, corners with three equivalent Li(1)O4 tetrahedra, and edges with three equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 50-58°. All Mn(1)-O(1) bond lengths are 2.14 Å. All Mn(1)-O(2) bond lengths are 2.30 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 Mn(1) atom. In the second O site, O(2) is bonded to one Li(1), two equivalent V(1), and one Mn(1) atom to form distorted OLiMnV2 tetrahedra that share corners with two equivalent O(2)LiMnV2 tetrahedra, corners with two equivalent O(4)LiV3 tetrahedra, and edges with two equivalent O(2)LiMnV2 tetrahedra. In the third O site, O(3) is bonded in a distorted rectangular see-saw-like geometry to one Li(1) and three equivalent V(1) atoms. In the fourth O site, O(4) is bonded to one Li(2) and three equivalent V(1) atoms to form distorted corner-sharing OLiV3 tetrahedra.