LiTiSi2O6 is Esseneite structured and crystallizes in the monoclinic C2/c space group. Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with four equivalent Si(1)O4 tetrahedra, edges with three equivalent Ti(1)O6 octahedra, and edges with two equivalent Si(1)O4 tetrahedra. Ti(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form TiO6 octahedra that share corners with six equivalent Si(1)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. Si(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form SiO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Ti(1)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-61°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1) and 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 rectangular see-saw-like geometry to one Li(1), two equivalent Ti(1), and one Si(1) atom.
LiTiSi2O6 is Esseneite structured and crystallizes in the monoclinic C2/c space group. Li(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted LiO6 octahedra that share corners with four equivalent Si(1)O4 tetrahedra, edges with three equivalent Ti(1)O6 octahedra, and edges with two equivalent Si(1)O4 tetrahedra. Both Li(1)-O(1) bond lengths are 2.37 Å. Both Li(1)-O(2) bond lengths are 2.19 Å. Both Li(1)-O(3) bond lengths are 2.10 Å. Ti(1) is bonded to two equivalent O(2) and four equivalent O(3) atoms to form TiO6 octahedra that share corners with six equivalent Si(1)O4 tetrahedra, edges with two equivalent Ti(1)O6 octahedra, and edges with three equivalent Li(1)O6 octahedra. Both Ti(1)-O(2) bond lengths are 1.97 Å. There are two shorter (2.12 Å) and two longer (2.13 Å) Ti(1)-O(3) bond lengths. Si(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form SiO4 tetrahedra that share corners with two equivalent Li(1)O6 octahedra, corners with three equivalent Ti(1)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Li(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 29-61°. The Si(1)-O(2) bond length is 1.61 Å. The Si(1)-O(3) bond length is 1.65 Å. Both Si(1)-O(1) bond lengths are 1.65 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(1) and 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 rectangular see-saw-like geometry to one Li(1), two equivalent Ti(1), and one Si(1) atom.