Bi2TiO5 crystallizes in the orthorhombic Cmcm space group. Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted corner-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles are 31°. Bi(1) is bonded in a 6-coordinate geometry to one O(3), two equivalent O(1), and three equivalent O(2) atoms. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Ti(1) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded to one Ti(1) and three equivalent Bi(1) atoms to form OTiBi3 tetrahedra that share corners with three equivalent O(2)TiBi3 tetrahedra,  a cornercorner with one O(3)Ti2Bi2 trigonal pyramid, edges with two equivalent O(2)TiBi3 tetrahedra, and edges with two equivalent O(3)Ti2Bi2 trigonal pyramids. In the third O site, O(3) is bonded to two equivalent Ti(1) and two equivalent Bi(1) atoms to form distorted OTi2Bi2 trigonal pyramids that share corners with two equivalent O(2)TiBi3 tetrahedra, corners with two equivalent O(3)Ti2Bi2 trigonal pyramids, and edges with four equivalent O(2)TiBi3 tetrahedra.
Bi2TiO5 crystallizes in the orthorhombic Cmcm space group. Ti(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(3) atoms to form distorted corner-sharing TiO6 octahedra. The corner-sharing octahedral tilt angles are 31°. Both Ti(1)-O(1) bond lengths are 1.84 Å. Both Ti(1)-O(2) bond lengths are 2.22 Å. Both Ti(1)-O(3) bond lengths are 2.11 Å. Bi(1) is bonded in a 6-coordinate geometry to one O(3), two equivalent O(1), and three equivalent O(2) atoms. The Bi(1)-O(3) bond length is 2.59 Å. There is one shorter (2.25 Å) and one longer (2.58 Å) Bi(1)-O(1) bond length. There are two shorter (2.26 Å) and one longer (2.33 Å) Bi(1)-O(2) bond length. There are three inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Ti(1) and two equivalent Bi(1) atoms. In the second O site, O(2) is bonded to one Ti(1) and three equivalent Bi(1) atoms to form OTiBi3 tetrahedra that share corners with three equivalent O(2)TiBi3 tetrahedra,  a cornercorner with one O(3)Ti2Bi2 trigonal pyramid, edges with two equivalent O(2)TiBi3 tetrahedra, and edges with two equivalent O(3)Ti2Bi2 trigonal pyramids. In the third O site, O(3) is bonded to two equivalent Ti(1) and two equivalent Bi(1) atoms to form distorted OTi2Bi2 trigonal pyramids that share corners with two equivalent O(2)TiBi3 tetrahedra, corners with two equivalent O(3)Ti2Bi2 trigonal pyramids, and edges with four equivalent O(2)TiBi3 tetrahedra.