Li2FeV3O8 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 Fe(1)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-60°. 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 Fe(1)O6 octahedra, and edges with four equivalent V(1)O6 octahedra. Fe(1) is bonded to six equivalent O(2) atoms to form FeO6 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 trigonal pyramids that share corners with three equivalent O(1)LiV3 trigonal pyramids, corners with nine equivalent O(2)LiV2Fe trigonal pyramids, and edges with three equivalent O(2)LiV2Fe trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), two equivalent V(1), and one Fe(1) atom to form distorted OLiV2Fe trigonal pyramids that share corners with three equivalent O(1)LiV3 trigonal pyramids, corners with nine equivalent O(2)LiV2Fe trigonal pyramids,  an edgeedge with one O(1)LiV3 trigonal pyramid, and edges with two equivalent O(2)LiV2Fe trigonal pyramids.
Li2FeV3O8 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 Fe(1)O6 octahedra and corners with nine equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 59-60°. The Li(1)-O(1) bond length is 1.94 Å. All Li(1)-O(2) bond lengths are 2.00 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 Fe(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 1.98 Å. Fe(1) is bonded to six equivalent O(2) atoms to form FeO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra and edges with six equivalent V(1)O6 octahedra. All Fe(1)-O(2) bond lengths are 2.01 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 trigonal pyramids that share corners with three equivalent O(1)LiV3 trigonal pyramids, corners with nine equivalent O(2)LiV2Fe trigonal pyramids, and edges with three equivalent O(2)LiV2Fe trigonal pyramids. In the second O site, O(2) is bonded to one Li(1), two equivalent V(1), and one Fe(1) atom to form distorted OLiV2Fe trigonal pyramids that share corners with three equivalent O(1)LiV3 trigonal pyramids, corners with nine equivalent O(2)LiV2Fe trigonal pyramids,  an edgeedge with one O(1)LiV3 trigonal pyramid, and edges with two equivalent O(2)LiV2Fe trigonal pyramids.