Ti2V(PO4)3 crystallizes in the trigonal R-3c space group. Ti(1) 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 V(1)O6 octahedra. V(1) is bonded to six equivalent O(2) atoms to form distorted VO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and faces with two equivalent 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 V(1)O6 octahedra and corners with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-48°. There are two inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ti(1), one V(1), and one P(1) atom.
Ti2V(PO4)3 crystallizes in the trigonal R-3c space group. Ti(1) 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 V(1)O6 octahedra. All Ti(1)-O(1) bond lengths are 1.93 Å. All Ti(1)-O(2) bond lengths are 2.08 Å. V(1) is bonded to six equivalent O(2) atoms to form distorted VO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and faces with two equivalent Ti(1)O6 octahedra. All V(1)-O(2) bond lengths are 2.22 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 V(1)O6 octahedra and corners with four equivalent Ti(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 26-48°. Both P(1)-O(1) bond lengths are 1.53 Å. Both P(1)-O(2) bond lengths are 1.56 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(1) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ti(1), one V(1), and one P(1) atom.