Ti2V3Cr(PO4)6 crystallizes in the trigonal R3 space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent O(2) and three equivalent O(6) atoms to form distorted TiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one V(2)O6 octahedra, and  a faceface with one Cr(1)O6 octahedra. In the second Ti site, Ti(2) is bonded to three equivalent O(4) and three equivalent O(7) atoms to form distorted TiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one V(1)O6 octahedra, and  a faceface with one V(3)O6 octahedra. There are three inequivalent V sites. In the first V site, V(1) is bonded to three equivalent O(4) and three equivalent O(8) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Ti(2)O6 octahedra. In the second V site, V(2) is bonded to three equivalent O(2) and three equivalent O(5) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Ti(1)O6 octahedra. In the third V site, V(3) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Ti(2)O6 octahedra. Cr(1) is bonded to three equivalent O(3) and three equivalent O(6) atoms to form CrO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Ti(1)O6 octahedra. There are two inequivalent P sites. In the first P site, 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  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-53°. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-52°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(3) 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(2), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ti(2), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ti(1), one Cr(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ti(2), one V(3), and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom.
Ti2V3Cr(PO4)6 crystallizes in the trigonal R3 space group. There are two inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent O(2) and three equivalent O(6) atoms to form distorted TiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one V(2)O6 octahedra, and  a faceface with one Cr(1)O6 octahedra. All Ti(1)-O(2) bond lengths are 2.08 Å. All Ti(1)-O(6) bond lengths are 2.13 Å. In the second Ti site, Ti(2) is bonded to three equivalent O(4) and three equivalent O(7) atoms to form distorted TiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one V(1)O6 octahedra, and  a faceface with one V(3)O6 octahedra. All Ti(2)-O(4) bond lengths are 2.11 Å. All Ti(2)-O(7) bond lengths are 2.09 Å. There are three inequivalent V sites. In the first V site, V(1) is bonded to three equivalent O(4) and three equivalent O(8) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Ti(2)O6 octahedra. All V(1)-O(4) bond lengths are 2.10 Å. All V(1)-O(8) bond lengths are 1.98 Å. In the second V site, V(2) is bonded to three equivalent O(2) and three equivalent O(5) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Ti(1)O6 octahedra. All V(2)-O(2) bond lengths are 2.09 Å. All V(2)-O(5) bond lengths are 1.97 Å. In the third V site, V(3) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Ti(2)O6 octahedra. All V(3)-O(1) bond lengths are 1.98 Å. All V(3)-O(7) bond lengths are 2.09 Å. Cr(1) is bonded to three equivalent O(3) and three equivalent O(6) atoms to form CrO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one Ti(1)O6 octahedra. All Cr(1)-O(3) bond lengths are 1.96 Å. All Cr(1)-O(6) bond lengths are 2.07 Å. There are two inequivalent P sites. In the first P site, 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  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-53°. The P(1)-O(1) bond length is 1.51 Å. The P(1)-O(2) bond length is 1.59 Å. The P(1)-O(3) bond length is 1.51 Å. The P(1)-O(4) bond length is 1.59 Å. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Ti(2)O6 octahedra,  a cornercorner with one V(1)O6 octahedra,  a cornercorner with one V(2)O6 octahedra,  a cornercorner with one V(3)O6 octahedra, and  a cornercorner with one Cr(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 28-52°. The P(2)-O(5) bond length is 1.51 Å. The P(2)-O(6) bond length is 1.59 Å. The P(2)-O(7) bond length is 1.59 Å. The P(2)-O(8) bond length is 1.51 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one V(3) 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(2), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Cr(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ti(2), one V(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one V(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ti(1), one Cr(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ti(2), one V(3), and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one V(1) and one P(2) atom.