Ti3V2Mn(PO4)6 crystallizes in the trigonal R3 space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent O(4) and three equivalent O(8) atoms to form TiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. In the second Ti site, Ti(2) is bonded to three equivalent O(2) and three equivalent O(5) atoms to form TiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one V(1)O6 octahedra. In the third Ti site, Ti(3) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form TiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. There are two inequivalent V sites. In the first V site, V(1) is bonded to three equivalent O(2) and three equivalent O(6) atoms to form distorted VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one Ti(2)O6 octahedra, and  a faceface with one Mn(1)O6 octahedra. In the second V site, V(2) is bonded in a 6-coordinate geometry to three equivalent O(4) and three equivalent O(7) atoms. Mn(1) is bonded to three equivalent O(3) and three equivalent O(6) atoms to form distorted MnO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one V(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 Ti(3)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, and  a cornercorner with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-50°. 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 Ti(3)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, and  a cornercorner with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-53°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(3) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ti(2), one V(1), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ti(1), one V(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(1), one Mn(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ti(3), one V(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom.
Ti3V2Mn(PO4)6 crystallizes in the trigonal R3 space group. There are three inequivalent Ti sites. In the first Ti site, Ti(1) is bonded to three equivalent O(4) and three equivalent O(8) atoms to form TiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. All Ti(1)-O(4) bond lengths are 2.03 Å. All Ti(1)-O(8) bond lengths are 1.88 Å. In the second Ti site, Ti(2) is bonded to three equivalent O(2) and three equivalent O(5) atoms to form TiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one V(1)O6 octahedra. All Ti(2)-O(2) bond lengths are 2.08 Å. All Ti(2)-O(5) bond lengths are 1.91 Å. In the third Ti site, Ti(3) is bonded to three equivalent O(1) and three equivalent O(7) atoms to form TiO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra and corners with three equivalent P(2)O4 tetrahedra. All Ti(3)-O(1) bond lengths are 1.89 Å. All Ti(3)-O(7) bond lengths are 2.10 Å. There are two inequivalent V sites. In the first V site, V(1) is bonded to three equivalent O(2) and three equivalent O(6) atoms to form distorted VO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one Ti(2)O6 octahedra, and  a faceface with one Mn(1)O6 octahedra. All V(1)-O(2) bond lengths are 2.19 Å. All V(1)-O(6) bond lengths are 2.18 Å. In the second V site, V(2) is bonded in a 6-coordinate geometry to three equivalent O(4) and three equivalent O(7) atoms. All V(2)-O(4) bond lengths are 2.24 Å. All V(2)-O(7) bond lengths are 2.22 Å. Mn(1) is bonded to three equivalent O(3) and three equivalent O(6) atoms to form distorted MnO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  a faceface with one V(1)O6 octahedra. All Mn(1)-O(3) bond lengths are 2.05 Å. All Mn(1)-O(6) bond lengths are 2.22 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 Ti(3)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, and  a cornercorner with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 23-50°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.49 Å. The P(1)-O(4) bond length is 1.57 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 Ti(3)O6 octahedra,  a cornercorner with one V(1)O6 octahedra, and  a cornercorner with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-53°. The P(2)-O(5) bond length is 1.56 Å. The P(2)-O(6) bond length is 1.52 Å. The P(2)-O(7) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.55 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Ti(3) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Ti(2), one V(1), and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Ti(1), one V(2), and one P(1) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Ti(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one V(1), one Mn(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Ti(3), one V(2), and one P(2) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom.