CaTiV(PO4)3 crystallizes in the trigonal R3c space group. Ca(1) is bonded in a distorted hexagonal planar geometry to three equivalent O(2) and three equivalent O(3) atoms. Ti(1) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form TiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. V(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-43°. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one Ti(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(1) atom.
CaTiV(PO4)3 crystallizes in the trigonal R3c space group. Ca(1) is bonded in a distorted hexagonal planar geometry to three equivalent O(2) and three equivalent O(3) atoms. All Ca(1)-O(2) bond lengths are 2.41 Å. All Ca(1)-O(3) bond lengths are 2.40 Å. Ti(1) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form TiO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. All Ti(1)-O(2) bond lengths are 2.08 Å. All Ti(1)-O(4) bond lengths are 1.90 Å. V(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form VO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra. All V(1)-O(1) bond lengths are 1.97 Å. All V(1)-O(3) bond lengths are 2.05 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Ti(1)O6 octahedra and corners with two equivalent V(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 24-43°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.54 Å. The P(1)-O(4) bond length is 1.57 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(1) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ca(1), one Ti(1), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Ca(1), one V(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(1) atom.