LiTi(Si2O5)2 crystallizes in the monoclinic P2/c space group. Li(1) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and edges with two equivalent Ti(1)O4 tetrahedra. Ti(1) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form distorted TiO4 tetrahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and edges with two equivalent Li(1)O4 tetrahedra. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form SiO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Ti(1)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra, and corners with two equivalent Si(2)O4 tetrahedra. In the second Si site, Si(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Ti(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and corners with two equivalent Si(1)O4 tetrahedra. There are six inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to two equivalent Si(1) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one Ti(1), and one Si(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one Ti(1), and one Si(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(2) atom. In the sixth O site, O(6) is bonded in a linear geometry to two equivalent Si(2) atoms.
LiTi(Si2O5)2 crystallizes in the monoclinic P2/c space group. Li(1) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form distorted LiO4 tetrahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and edges with two equivalent Ti(1)O4 tetrahedra. Both Li(1)-O(2) bond lengths are 1.95 Å. Both Li(1)-O(3) bond lengths are 1.94 Å. Ti(1) is bonded to two equivalent O(2) and two equivalent O(3) atoms to form distorted TiO4 tetrahedra that share corners with two equivalent Si(1)O4 tetrahedra, corners with two equivalent Si(2)O4 tetrahedra, and edges with two equivalent Li(1)O4 tetrahedra. Both Ti(1)-O(2) bond lengths are 1.92 Å. Both Ti(1)-O(3) bond lengths are 1.92 Å. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form SiO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Ti(1)O4 tetrahedra,  a cornercorner with one Si(1)O4 tetrahedra, and corners with two equivalent Si(2)O4 tetrahedra. The Si(1)-O(1) bond length is 1.62 Å. The Si(1)-O(2) bond length is 1.63 Å. The Si(1)-O(4) bond length is 1.64 Å. The Si(1)-O(5) bond length is 1.64 Å. In the second Si site, Si(2) is bonded to one O(3), one O(4), one O(5), and one O(6) atom to form SiO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Ti(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and corners with two equivalent Si(1)O4 tetrahedra. The Si(2)-O(3) bond length is 1.63 Å. The Si(2)-O(4) bond length is 1.64 Å. The Si(2)-O(5) bond length is 1.64 Å. The Si(2)-O(6) bond length is 1.62 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a linear geometry to two equivalent Si(1) atoms. In the second O site, O(2) is bonded in a distorted T-shaped geometry to one Li(1), one Ti(1), and one Si(1) atom. In the third O site, O(3) is bonded in a distorted T-shaped geometry to one Li(1), one Ti(1), and one Si(2) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Si(1) and one Si(2) atom. In the sixth O site, O(6) is bonded in a linear geometry to two equivalent Si(2) atoms.