TiSi2O6 crystallizes in the monoclinic C2/c space group. Ti(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted TiO6 octahedra that share corners with six equivalent Si(1)O4 tetrahedra and edges with two equivalent Ti(1)O6 octahedra. Si(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form SiO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra and corners with two equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-58°. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Ti(1) and one Si(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ti(1) and one Si(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent Si(1) atoms.
TiSi2O6 crystallizes in the monoclinic C2/c space group. Ti(1) is bonded to two equivalent O(2) and four equivalent O(1) atoms to form distorted TiO6 octahedra that share 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 1.84 Å. There are two shorter (2.00 Å) and two longer (2.17 Å) Ti(1)-O(1) bond lengths. Si(1) is bonded to one O(1), one O(2), and two equivalent O(3) atoms to form SiO4 tetrahedra that share corners with three equivalent Ti(1)O6 octahedra and corners with two equivalent Si(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 30-58°. The Si(1)-O(1) bond length is 1.66 Å. The Si(1)-O(2) bond length is 1.64 Å. There is one shorter (1.62 Å) and one longer (1.63 Å) Si(1)-O(3) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to two equivalent Ti(1) and one Si(1) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Ti(1) and one Si(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to two equivalent Si(1) atoms.