Li2Fe3SnO8 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 Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-60°. 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 Sn(1)O4 tetrahedra, and edges with six equivalent Fe(1)O6 octahedra. Fe(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form FeO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Sn(1)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent Fe(1)O6 octahedra. Sn(1) is bonded to one O(4) and three equivalent O(3) atoms to form SnO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with nine equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-61°. 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(1) and three equivalent Fe(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 Fe(1) atoms. In the third O site, O(3) is bonded to one Li(2), two equivalent Fe(1), and one Sn(1) atom to form distorted OLiFe2Sn tetrahedra that share corners with two equivalent O(3)LiFe2Sn tetrahedra,  a cornercorner with one O(4)Fe3Sn trigonal pyramid, edges with two equivalent O(3)LiFe2Sn tetrahedra, and  an edgeedge with one O(4)Fe3Sn trigonal pyramid. In the fourth O site, O(4) is bonded to three equivalent Fe(1) and one Sn(1) atom to form a mixture of distorted edge and corner-sharing OFe3Sn trigonal pyramids.
Li2Fe3SnO8 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 Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 55-60°. The Li(1)-O(1) bond length is 2.01 Å. All Li(1)-O(2) bond lengths are 2.00 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 Sn(1)O4 tetrahedra, and edges with six equivalent Fe(1)O6 octahedra. All Li(2)-O(2) bond lengths are 2.11 Å. All Li(2)-O(3) bond lengths are 2.11 Å. Fe(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form FeO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Sn(1)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, and edges with four equivalent Fe(1)O6 octahedra. The Fe(1)-O(1) bond length is 2.03 Å. The Fe(1)-O(4) bond length is 2.15 Å. Both Fe(1)-O(2) bond lengths are 1.94 Å. Both Fe(1)-O(3) bond lengths are 2.07 Å. Sn(1) is bonded to one O(4) and three equivalent O(3) atoms to form SnO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra and corners with nine equivalent Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 58-61°. The Sn(1)-O(4) bond length is 2.02 Å. All Sn(1)-O(3) bond lengths are 1.99 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(1) and three equivalent Fe(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 Fe(1) atoms. In the third O site, O(3) is bonded to one Li(2), two equivalent Fe(1), and one Sn(1) atom to form distorted OLiFe2Sn tetrahedra that share corners with two equivalent O(3)LiFe2Sn tetrahedra,  a cornercorner with one O(4)Fe3Sn trigonal pyramid, edges with two equivalent O(3)LiFe2Sn tetrahedra, and  an edgeedge with one O(4)Fe3Sn trigonal pyramid. In the fourth O site, O(4) is bonded to three equivalent Fe(1) and one Sn(1) atom to form a mixture of distorted edge and corner-sharing OFe3Sn trigonal pyramids.