Tl2TiO3 crystallizes in the orthorhombic Pnma space group. Ti(1) is bonded to one O(2), one O(3), and three equivalent O(1) atoms to form a mixture of distorted corner and edge-sharing TiO5 trigonal bipyramids. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a distorted T-shaped geometry to one O(3) and two equivalent O(2) atoms. In the second Tl site, Tl(2) is bonded in a 3-coordinate geometry to one O(2) and two equivalent O(3) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to three equivalent Ti(1) atoms. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ti(1), one Tl(2), and two equivalent Tl(1) atoms. In the third O site, O(3) is bonded to one Ti(1), one Tl(1), and two equivalent Tl(2) atoms to form distorted corner-sharing OTiTl3 tetrahedra.
Tl2TiO3 crystallizes in the orthorhombic Pnma space group. Ti(1) is bonded to one O(2), one O(3), and three equivalent O(1) atoms to form a mixture of distorted corner and edge-sharing TiO5 trigonal bipyramids. The Ti(1)-O(2) bond length is 1.80 Å. The Ti(1)-O(3) bond length is 1.82 Å. There are two shorter (1.97 Å) and one longer (2.02 Å) Ti(1)-O(1) bond length. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a distorted T-shaped geometry to one O(3) and two equivalent O(2) atoms. The Tl(1)-O(3) bond length is 2.44 Å. Both Tl(1)-O(2) bond lengths are 2.57 Å. In the second Tl site, Tl(2) is bonded in a 3-coordinate geometry to one O(2) and two equivalent O(3) atoms. The Tl(2)-O(2) bond length is 2.54 Å. Both Tl(2)-O(3) bond lengths are 2.52 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to three equivalent Ti(1) atoms. In the second O site, O(2) is bonded in a 4-coordinate geometry to one Ti(1), one Tl(2), and two equivalent Tl(1) atoms. In the third O site, O(3) is bonded to one Ti(1), one Tl(1), and two equivalent Tl(2) atoms to form distorted corner-sharing OTiTl3 tetrahedra.