Li3Ti(FeO2)4 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 two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Fe(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles are 4°. Ti(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form TiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles are 4°. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form FeO6 octahedra that share corners with six equivalent Fe(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the second Fe site, Fe(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form FeO6 octahedra that share corners with six equivalent Fe(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. In the third Fe site, Fe(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form FeO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), one Ti(1), and two equivalent Fe(3) atoms to form OLi3TiFe2 octahedra that share corners with six equivalent O(1)Li3TiFe2 octahedra, edges with four equivalent O(3)Li2Fe4 octahedra, and edges with eight equivalent O(2)Li2TiFe3 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Ti(1), one Fe(1), one Fe(2), and one Fe(3) atom to form OLi2TiFe3 octahedra that share corners with six equivalent O(2)Li2TiFe3 octahedra, edges with four equivalent O(3)Li2Fe4 octahedra, edges with four equivalent O(2)Li2TiFe3 octahedra, and edges with four equivalent O(1)Li3TiFe2 octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to two equivalent Li(1), one Fe(1), one Fe(2), and two equivalent Fe(3) atoms to form OLi2Fe4 octahedra that share corners with six equivalent O(3)Li2Fe4 octahedra, edges with four equivalent O(1)Li3TiFe2 octahedra, and edges with eight equivalent O(2)Li2TiFe3 octahedra. The corner-sharing octahedra are not tilted.
Li3Ti(FeO2)4 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 two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share corners with six equivalent Fe(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. Both Li(1)-O(1) bond lengths are 2.20 Å. Both Li(1)-O(2) bond lengths are 2.07 Å. Both Li(1)-O(3) bond lengths are 2.15 Å. In the second Li site, Li(2) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with six equivalent Ti(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles are 4°. Both Li(2)-O(1) bond lengths are 2.25 Å. All Li(2)-O(2) bond lengths are 2.27 Å. Ti(1) is bonded to two equivalent O(1) and four equivalent O(2) atoms to form TiO6 octahedra that share corners with six equivalent Li(2)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles are 4°. Both Ti(1)-O(1) bond lengths are 1.97 Å. All Ti(1)-O(2) bond lengths are 2.03 Å. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form FeO6 octahedra that share corners with six equivalent Fe(2)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. Both Fe(1)-O(3) bond lengths are 2.07 Å. All Fe(1)-O(2) bond lengths are 2.08 Å. In the second Fe site, Fe(2) is bonded to two equivalent O(3) and four equivalent O(2) atoms to form FeO6 octahedra that share corners with six equivalent Fe(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with four equivalent Li(1)O6 octahedra, and edges with four equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 0-7°. Both Fe(2)-O(3) bond lengths are 2.15 Å. All Fe(2)-O(2) bond lengths are 2.22 Å. In the third Fe site, Fe(3) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form FeO6 octahedra that share corners with six equivalent Li(1)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Ti(1)O6 octahedra, edges with two equivalent Fe(1)O6 octahedra, edges with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-8°. Both Fe(3)-O(1) bond lengths are 2.11 Å. Both Fe(3)-O(2) bond lengths are 2.15 Å. Both Fe(3)-O(3) bond lengths are 2.15 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to one Li(2), two equivalent Li(1), one Ti(1), and two equivalent Fe(3) atoms to form OLi3TiFe2 octahedra that share corners with six equivalent O(1)Li3TiFe2 octahedra, edges with four equivalent O(3)Li2Fe4 octahedra, and edges with eight equivalent O(2)Li2TiFe3 octahedra. The corner-sharing octahedra are not tilted. In the second O site, O(2) is bonded to one Li(1), one Li(2), one Ti(1), one Fe(1), one Fe(2), and one Fe(3) atom to form OLi2TiFe3 octahedra that share corners with six equivalent O(2)Li2TiFe3 octahedra, edges with four equivalent O(3)Li2Fe4 octahedra, edges with four equivalent O(2)Li2TiFe3 octahedra, and edges with four equivalent O(1)Li3TiFe2 octahedra. The corner-sharing octahedra are not tilted. In the third O site, O(3) is bonded to two equivalent Li(1), one Fe(1), one Fe(2), and two equivalent Fe(3) atoms to form OLi2Fe4 octahedra that share corners with six equivalent O(3)Li2Fe4 octahedra, edges with four equivalent O(1)Li3TiFe2 octahedra, and edges with eight equivalent O(2)Li2TiFe3 octahedra. The corner-sharing octahedra are not tilted.