Li6TiFe5O12 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, corners with three equivalent Fe(3)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and  a faceface with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-52°. In the second Li site, Li(2) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with six equivalent Fe(3)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and  a faceface with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-50°. Ti(1) is bonded to two equivalent O(2) and four equivalent O(4) atoms to form TiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with six equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles are 1°. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form FeO6 octahedra that share corners with twelve equivalent Li(1)O6 octahedra, edges with six equivalent Fe(3)O6 octahedra, and faces with two equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. In the second Fe site, Fe(2) is bonded to two equivalent O(2) and four equivalent O(4) atoms to form FeO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent Ti(1)O6 octahedra, edges with three equivalent Fe(2)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. In the third Fe site, Fe(3) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form distorted FeO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, corners with six equivalent Li(2)O6 octahedra, edges with three equivalent Fe(1)O6 octahedra, edges with three equivalent Fe(3)O6 octahedra, and faces with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-50°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), one Fe(1), and two equivalent Fe(3) atoms. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), one Ti(1), and two equivalent Fe(2) atoms to form a mixture of edge and corner-sharing OLi3TiFe2 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), one Fe(1), and two equivalent Fe(3) atoms. In the fourth O site, O(4) is bonded to one Li(2), two equivalent Li(1), one Ti(1), and two equivalent Fe(2) atoms to form a mixture of edge and corner-sharing OLi3TiFe2 octahedra. The corner-sharing octahedral tilt angles range from 0-4°.
Li6TiFe5O12 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form distorted LiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with three equivalent Fe(1)O6 octahedra, corners with three equivalent Fe(3)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, and  a faceface with one Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-52°. The Li(1)-O(1) bond length is 2.36 Å. The Li(1)-O(2) bond length is 2.11 Å. There is one shorter (2.11 Å) and one longer (2.14 Å) Li(1)-O(3) bond length. There is one shorter (2.11 Å) and one longer (2.15 Å) Li(1)-O(4) bond length. In the second Li site, Li(2) is bonded to one O(1), one O(2), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Fe(2)O6 octahedra, corners with six equivalent Fe(3)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, edges with six equivalent Li(1)O6 octahedra, and  a faceface with one Fe(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 1-50°. The Li(2)-O(1) bond length is 2.17 Å. The Li(2)-O(2) bond length is 2.23 Å. Both Li(2)-O(3) bond lengths are 2.28 Å. Both Li(2)-O(4) bond lengths are 2.08 Å. Ti(1) is bonded to two equivalent O(2) and four equivalent O(4) atoms to form TiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with six equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles are 1°. Both Ti(1)-O(2) bond lengths are 2.00 Å. All Ti(1)-O(4) bond lengths are 1.99 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form FeO6 octahedra that share corners with twelve equivalent Li(1)O6 octahedra, edges with six equivalent Fe(3)O6 octahedra, and faces with two equivalent Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 46-52°. Both Fe(1)-O(1) bond lengths are 2.18 Å. All Fe(1)-O(3) bond lengths are 2.04 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(2) and four equivalent O(4) atoms to form FeO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with three equivalent Ti(1)O6 octahedra, edges with three equivalent Fe(2)O6 octahedra, and edges with four equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 5-7°. Both Fe(2)-O(2) bond lengths are 2.08 Å. There are two shorter (2.09 Å) and two longer (2.10 Å) Fe(2)-O(4) bond lengths. In the third Fe site, Fe(3) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form distorted FeO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, corners with six equivalent Li(2)O6 octahedra, edges with three equivalent Fe(1)O6 octahedra, edges with three equivalent Fe(3)O6 octahedra, and faces with two equivalent Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-50°. Both Fe(3)-O(1) bond lengths are 1.94 Å. There are two shorter (1.91 Å) and two longer (2.26 Å) Fe(3)-O(3) bond lengths. There are four inequivalent O sites. In the first O site, O(1) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), one Fe(1), and two equivalent Fe(3) atoms. In the second O site, O(2) is bonded to one Li(2), two equivalent Li(1), one Ti(1), and two equivalent Fe(2) atoms to form a mixture of edge and corner-sharing OLi3TiFe2 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the third O site, O(3) is bonded in a 6-coordinate geometry to one Li(2), two equivalent Li(1), one Fe(1), and two equivalent Fe(3) atoms. In the fourth O site, O(4) is bonded to one Li(2), two equivalent Li(1), one Ti(1), and two equivalent Fe(2) atoms to form a mixture of edge and corner-sharing OLi3TiFe2 octahedra. The corner-sharing octahedral tilt angles range from 0-4°.