TiPO4 crystallizes in the trigonal R-3c space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to six equivalent O(2) atoms to form distorted TiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and faces with two equivalent Ti(2)O6 octahedra. In the second Ti site, Ti(2) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form TiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and  a faceface with one Ti(1)O6 octahedra. P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra and corners with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-50°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ti(1), one Ti(2), and one P(1) atom.
TiPO4 crystallizes in the trigonal R-3c space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to six equivalent O(2) atoms to form distorted TiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and faces with two equivalent Ti(2)O6 octahedra. All Ti(1)-O(2) bond lengths are 2.17 Å. In the second Ti site, Ti(2) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form TiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and  a faceface with one Ti(1)O6 octahedra. All Ti(2)-O(1) bond lengths are 1.95 Å. All Ti(2)-O(2) bond lengths are 2.09 Å. P(1) is bonded to two equivalent O(1) and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra and corners with four equivalent Ti(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 27-50°. Both P(1)-O(1) bond lengths are 1.53 Å. Both P(1)-O(2) bond lengths are 1.57 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ti(1), one Ti(2), and one P(1) atom.