Li7Ti3(SiO6)2 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Si(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent Si(1)O6 octahedra, and edges with six equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. In the second Li site, Li(2) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with six equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles are 14°. In the third Li site, Li(3) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Si(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent Si(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with six equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles are 2°. In the second Ti site, Ti(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with three equivalent Ti(1)O6 octahedra, edges with three equivalent Ti(2)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles are 2°. Si(1) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form SiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, edges with three equivalent Si(1)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles are 12°. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(3), one Ti(1), and two equivalent Ti(2) atoms to form OLi3Ti3 octahedra that share  a cornercorner with one O(1)Li3Ti3 octahedra,  a cornercorner with one O(4)Li4Si2 octahedra, corners with two equivalent O(3)Li3Ti3 octahedra, corners with two equivalent O(2)Li4Si2 octahedra,  an edgeedge with one O(1)Li3Ti3 octahedra,  an edgeedge with one O(4)Li4Si2 octahedra, edges with two equivalent O(2)Li4Si2 octahedra, and edges with eight equivalent O(3)Li3Ti3 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second O site, O(2) is bonded to one Li(1), one Li(2), two equivalent Li(3), and two equivalent Si(1) atoms to form OLi4Si2 octahedra that share  a cornercorner with one O(1)Li3Ti3 octahedra,  a cornercorner with one O(4)Li4Si2 octahedra, corners with two equivalent O(3)Li3Ti3 octahedra, corners with two equivalent O(2)Li4Si2 octahedra,  an edgeedge with one O(1)Li3Ti3 octahedra, edges with two equivalent O(3)Li3Ti3 octahedra, edges with four equivalent O(4)Li4Si2 octahedra, and edges with five equivalent O(2)Li4Si2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(3), one Ti(1), and two equivalent Ti(2) atoms to form OLi3Ti3 octahedra that share  a cornercorner with one O(1)Li3Ti3 octahedra,  a cornercorner with one O(4)Li4Si2 octahedra, corners with two equivalent O(3)Li3Ti3 octahedra, corners with two equivalent O(2)Li4Si2 octahedra,  an edgeedge with one O(4)Li4Si2 octahedra, edges with two equivalent O(2)Li4Si2 octahedra, edges with four equivalent O(1)Li3Ti3 octahedra, and edges with five equivalent O(3)Li3Ti3 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), two equivalent Li(3), and two equivalent Si(1) atoms to form OLi4Si2 octahedra that share  a cornercorner with one O(1)Li3Ti3 octahedra,  a cornercorner with one O(4)Li4Si2 octahedra, corners with two equivalent O(3)Li3Ti3 octahedra, corners with two equivalent O(2)Li4Si2 octahedra,  an edgeedge with one O(1)Li3Ti3 octahedra,  an edgeedge with one O(4)Li4Si2 octahedra, edges with two equivalent O(3)Li3Ti3 octahedra, and edges with eight equivalent O(2)Li4Si2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°.
Li7Ti3(SiO6)2 is Caswellsilverite-derived structured and crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Si(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent Si(1)O6 octahedra, and edges with six equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. The Li(1)-O(1) bond length is 2.07 Å. The Li(1)-O(4) bond length is 2.01 Å. Both Li(1)-O(2) bond lengths are 2.21 Å. Both Li(1)-O(3) bond lengths are 2.12 Å. In the second Li site, Li(2) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with six equivalent Si(1)O6 octahedra. The corner-sharing octahedral tilt angles are 14°. Both Li(2)-O(4) bond lengths are 2.09 Å. All Li(2)-O(2) bond lengths are 2.09 Å. In the third Li site, Li(3) is bonded to one O(1), one O(4), two equivalent O(2), and two equivalent O(3) atoms to form LiO6 octahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Ti(1)O6 octahedra, corners with two equivalent Ti(2)O6 octahedra, corners with two equivalent Si(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Ti(1)O6 octahedra, edges with two equivalent Ti(2)O6 octahedra, edges with two equivalent Si(1)O6 octahedra, edges with three equivalent Li(1)O6 octahedra, and edges with three equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 2-14°. The Li(3)-O(1) bond length is 2.06 Å. The Li(3)-O(4) bond length is 2.21 Å. There is one shorter (2.01 Å) and one longer (2.21 Å) Li(3)-O(2) bond length. There is one shorter (2.11 Å) and one longer (2.12 Å) Li(3)-O(3) bond length. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with four equivalent Li(3)O6 octahedra, and edges with six equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles are 2°. Both Ti(1)-O(1) bond lengths are 2.05 Å. All Ti(1)-O(3) bond lengths are 2.04 Å. In the second Ti site, Ti(2) is bonded to two equivalent O(1) and four equivalent O(3) atoms to form TiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with three equivalent Ti(1)O6 octahedra, edges with three equivalent Ti(2)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles are 2°. Both Ti(2)-O(1) bond lengths are 2.05 Å. All Ti(2)-O(3) bond lengths are 2.04 Å. Si(1) is bonded to two equivalent O(4) and four equivalent O(2) atoms to form SiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Li(3)O6 octahedra, edges with two equivalent Li(1)O6 octahedra, edges with three equivalent Li(2)O6 octahedra, edges with three equivalent Si(1)O6 octahedra, and edges with four equivalent Li(3)O6 octahedra. The corner-sharing octahedral tilt angles are 12°. Both Si(1)-O(4) bond lengths are 1.84 Å. All Si(1)-O(2) bond lengths are 1.84 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Li(3), one Ti(1), and two equivalent Ti(2) atoms to form OLi3Ti3 octahedra that share  a cornercorner with one O(1)Li3Ti3 octahedra,  a cornercorner with one O(4)Li4Si2 octahedra, corners with two equivalent O(3)Li3Ti3 octahedra, corners with two equivalent O(2)Li4Si2 octahedra,  an edgeedge with one O(1)Li3Ti3 octahedra,  an edgeedge with one O(4)Li4Si2 octahedra, edges with two equivalent O(2)Li4Si2 octahedra, and edges with eight equivalent O(3)Li3Ti3 octahedra. The corner-sharing octahedral tilt angles range from 0-4°. In the second O site, O(2) is bonded to one Li(1), one Li(2), two equivalent Li(3), and two equivalent Si(1) atoms to form OLi4Si2 octahedra that share  a cornercorner with one O(1)Li3Ti3 octahedra,  a cornercorner with one O(4)Li4Si2 octahedra, corners with two equivalent O(3)Li3Ti3 octahedra, corners with two equivalent O(2)Li4Si2 octahedra,  an edgeedge with one O(1)Li3Ti3 octahedra, edges with two equivalent O(3)Li3Ti3 octahedra, edges with four equivalent O(4)Li4Si2 octahedra, and edges with five equivalent O(2)Li4Si2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°. In the third O site, O(3) is bonded to one Li(1), two equivalent Li(3), one Ti(1), and two equivalent Ti(2) atoms to form OLi3Ti3 octahedra that share  a cornercorner with one O(1)Li3Ti3 octahedra,  a cornercorner with one O(4)Li4Si2 octahedra, corners with two equivalent O(3)Li3Ti3 octahedra, corners with two equivalent O(2)Li4Si2 octahedra,  an edgeedge with one O(4)Li4Si2 octahedra, edges with two equivalent O(2)Li4Si2 octahedra, edges with four equivalent O(1)Li3Ti3 octahedra, and edges with five equivalent O(3)Li3Ti3 octahedra. The corner-sharing octahedral tilt angles range from 0-6°. In the fourth O site, O(4) is bonded to one Li(1), one Li(2), two equivalent Li(3), and two equivalent Si(1) atoms to form OLi4Si2 octahedra that share  a cornercorner with one O(1)Li3Ti3 octahedra,  a cornercorner with one O(4)Li4Si2 octahedra, corners with two equivalent O(3)Li3Ti3 octahedra, corners with two equivalent O(2)Li4Si2 octahedra,  an edgeedge with one O(1)Li3Ti3 octahedra,  an edgeedge with one O(4)Li4Si2 octahedra, edges with two equivalent O(3)Li3Ti3 octahedra, and edges with eight equivalent O(2)Li4Si2 octahedra. The corner-sharing octahedral tilt angles range from 0-11°.