Li2Cr3FeO8 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 Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-64°. 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 Fe(1)O4 tetrahedra, and edges with six equivalent Cr(1)O6 octahedra. Cr(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Fe(1)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. Fe(1) is bonded to one O(4) and three equivalent O(3) atoms to form FeO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with nine equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 58°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1) and three equivalent Cr(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 Cr(1) atoms. In the third O site, O(3) is bonded to one Li(2), two equivalent Cr(1), and one Fe(1) atom to form distorted OLiCr2Fe trigonal pyramids that share  a cornercorner with one O(4)Cr3Fe trigonal pyramid, corners with two equivalent O(3)LiCr2Fe trigonal pyramids,  an edgeedge with one O(4)Cr3Fe trigonal pyramid, and edges with two equivalent O(3)LiCr2Fe trigonal pyramids. In the fourth O site, O(4) is bonded to three equivalent Cr(1) and one Fe(1) atom to form a mixture of distorted corner and edge-sharing OCr3Fe trigonal pyramids.
Li2Cr3FeO8 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 Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-64°. The Li(1)-O(1) bond length is 1.96 Å. All Li(1)-O(2) bond lengths are 1.98 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 Fe(1)O4 tetrahedra, and edges with six equivalent Cr(1)O6 octahedra. All Li(2)-O(2) bond lengths are 2.11 Å. All Li(2)-O(3) bond lengths are 2.07 Å. Cr(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form CrO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Fe(1)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent Cr(1)O6 octahedra. The Cr(1)-O(1) bond length is 1.98 Å. The Cr(1)-O(4) bond length is 2.06 Å. Both Cr(1)-O(2) bond lengths are 1.90 Å. Both Cr(1)-O(3) bond lengths are 2.03 Å. Fe(1) is bonded to one O(4) and three equivalent O(3) atoms to form FeO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with nine equivalent Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles are 58°. The Fe(1)-O(4) bond length is 1.97 Å. All Fe(1)-O(3) bond lengths are 1.91 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(1) and three equivalent Cr(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 Cr(1) atoms. In the third O site, O(3) is bonded to one Li(2), two equivalent Cr(1), and one Fe(1) atom to form distorted OLiCr2Fe trigonal pyramids that share  a cornercorner with one O(4)Cr3Fe trigonal pyramid, corners with two equivalent O(3)LiCr2Fe trigonal pyramids,  an edgeedge with one O(4)Cr3Fe trigonal pyramid, and edges with two equivalent O(3)LiCr2Fe trigonal pyramids. In the fourth O site, O(4) is bonded to three equivalent Cr(1) and one Fe(1) atom to form a mixture of distorted corner and edge-sharing OCr3Fe trigonal pyramids.