LiTiSiO4 crystallizes in the orthorhombic Pbcn space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form distorted LiO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra, corners with three equivalent Ti(2)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 66-71°. In the second Li site, Li(2) is bonded to two equivalent O(4) and two equivalent O(6) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent Ti(2)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 68-69°. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) 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(2)O6 octahedra. In the second Ti site, Ti(2) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(6) atoms to form TiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent Si(1)O4 tetrahedra, corners with three equivalent Si(2)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra, and  an edgeedge with one Ti(2)O6 octahedra. There are two inequivalent Si sites. In the first Si site, Si(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form SiO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra, corners with three equivalent Ti(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-53°. In the second Si site, Si(2) is bonded to two equivalent O(5) and two equivalent O(6) atoms to form SiO4 tetrahedra that share corners with six equivalent Ti(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-51°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one Ti(1), and one Si(1) atom. In the second O site, O(2) is bonded to one Li(1), one Ti(1), one Ti(2), and one Si(1) atom to form a mixture of distorted corner and edge-sharing OLiTi2Si tetrahedra. In the third O site, O(3) is bonded to one Li(1), one Ti(1), one Ti(2), and one Si(1) atom to form a mixture of distorted corner and edge-sharing OLiTi2Si tetrahedra. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(2), one Ti(2), and one Si(1) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(1), one Ti(2), and one Si(2) atom. In the sixth O site, O(6) is bonded to one Li(2), two equivalent Ti(2), and one Si(2) atom to form a mixture of distorted corner and edge-sharing OLiTi2Si tetrahedra.
LiTiSiO4 crystallizes in the orthorhombic Pbcn space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(3), and one O(5) atom to form distorted LiO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra, corners with three equivalent Ti(2)O6 octahedra,  a cornercorner with one Si(1)O4 tetrahedra,  a cornercorner with one Si(2)O4 tetrahedra, and  an edgeedge with one Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 66-71°. The Li(1)-O(1) bond length is 1.92 Å. The Li(1)-O(2) bond length is 2.16 Å. The Li(1)-O(3) bond length is 2.03 Å. The Li(1)-O(5) bond length is 1.90 Å. In the second Li site, Li(2) is bonded to two equivalent O(4) and two equivalent O(6) atoms to form distorted LiO4 tetrahedra that share corners with six equivalent Ti(2)O6 octahedra, corners with two equivalent Si(1)O4 tetrahedra, and  an edgeedge with one Si(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 68-69°. Both Li(2)-O(4) bond lengths are 1.89 Å. Both Li(2)-O(6) bond lengths are 2.05 Å. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) 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(2)O6 octahedra. Both Ti(1)-O(1) bond lengths are 1.97 Å. Both Ti(1)-O(2) bond lengths are 2.15 Å. Both Ti(1)-O(3) bond lengths are 2.15 Å. In the second Ti site, Ti(2) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(6) atoms to form TiO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent Li(2)O4 tetrahedra, corners with three equivalent Si(1)O4 tetrahedra, corners with three equivalent Si(2)O4 tetrahedra,  an edgeedge with one Ti(1)O6 octahedra, and  an edgeedge with one Ti(2)O6 octahedra. The Ti(2)-O(2) bond length is 2.18 Å. The Ti(2)-O(3) bond length is 2.19 Å. The Ti(2)-O(4) bond length is 1.98 Å. The Ti(2)-O(5) bond length is 1.98 Å. Both Ti(2)-O(6) bond lengths are 2.11 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(3), and one O(4) atom to form SiO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra, corners with three equivalent Ti(2)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one Li(2)O4 tetrahedra, and  an edgeedge with one Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-53°. The Si(1)-O(1) bond length is 1.63 Å. The Si(1)-O(2) bond length is 1.69 Å. The Si(1)-O(3) bond length is 1.67 Å. The Si(1)-O(4) bond length is 1.63 Å. In the second Si site, Si(2) is bonded to two equivalent O(5) and two equivalent O(6) atoms to form SiO4 tetrahedra that share corners with six equivalent Ti(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-51°. Both Si(2)-O(5) bond lengths are 1.62 Å. Both Si(2)-O(6) bond lengths are 1.67 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Li(1), one Ti(1), and one Si(1) atom. In the second O site, O(2) is bonded to one Li(1), one Ti(1), one Ti(2), and one Si(1) atom to form a mixture of distorted corner and edge-sharing OLiTi2Si tetrahedra. In the third O site, O(3) is bonded to one Li(1), one Ti(1), one Ti(2), and one Si(1) atom to form a mixture of distorted corner and edge-sharing OLiTi2Si tetrahedra. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Li(2), one Ti(2), and one Si(1) atom. In the fifth O site, O(5) is bonded in a trigonal planar geometry to one Li(1), one Ti(2), and one Si(2) atom. In the sixth O site, O(6) is bonded to one Li(2), two equivalent Ti(2), and one Si(2) atom to form a mixture of distorted corner and edge-sharing OLiTi2Si tetrahedra.