LiTiSiO4 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent Ti(1)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 68-69°. Ti(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form TiO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent Si(1)O4 tetrahedra, and edges with two equivalent Ti(1)O6 octahedra. Si(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form SiO4 tetrahedra that share corners with six equivalent Ti(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-52°. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Ti(1), and one Si(1) atom to form a mixture of distorted corner and edge-sharing OLiTi2Si tetrahedra. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Ti(1), and one Si(1) atom.
LiTiSiO4 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent Ti(1)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 68-69°. Both Li(1)-O(1) bond lengths are 2.07 Å. Both Li(1)-O(2) bond lengths are 1.89 Å. Ti(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form TiO6 octahedra that share corners with six equivalent Li(1)O4 tetrahedra, corners with six equivalent Si(1)O4 tetrahedra, and edges with two equivalent Ti(1)O6 octahedra. Both Ti(1)-O(2) bond lengths are 1.98 Å. All Ti(1)-O(1) bond lengths are 2.14 Å. Si(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form SiO4 tetrahedra that share corners with six equivalent Ti(1)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-52°. Both Si(1)-O(1) bond lengths are 1.68 Å. Both Si(1)-O(2) bond lengths are 1.63 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(1), two equivalent Ti(1), and one Si(1) atom to form a mixture of distorted corner and edge-sharing OLiTi2Si tetrahedra. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Ti(1), and one Si(1) atom.