TiMn3Fe2(PO4)6 crystallizes in the trigonal R3 space group. Ti(1) is bonded to three equivalent O(3) 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, and  a faceface with one Fe(1)O6 octahedra. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to three equivalent O(2) and three equivalent O(5) 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 Fe(1)O6 octahedra. In the second Mn site, Mn(2) is bonded to three equivalent O(1) and three equivalent O(4) 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 Fe(2)O6 octahedra. In the third Mn site, Mn(3) is bonded to three equivalent O(7) and three equivalent O(8) atoms to form 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 Fe(2)O6 octahedra. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to three equivalent O(2) and three equivalent O(6) atoms to form distorted FeO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one Ti(1)O6 octahedra, and  a faceface with one Mn(1)O6 octahedra. In the second Fe site, Fe(2) is bonded to three equivalent O(4) and three equivalent O(7) atoms to form distorted FeO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one Mn(2)O6 octahedra, and  a faceface with one Mn(3)O6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra, and  a cornercorner with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-51°. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra, and  a cornercorner with one Fe(2)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 Mn(2) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Mn(1), one Fe(1), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mn(2), one Fe(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ti(1), one Fe(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mn(3), one Fe(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Mn(3) and one P(2) atom.
TiMn3Fe2(PO4)6 crystallizes in the trigonal R3 space group. Ti(1) is bonded to three equivalent O(3) 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, and  a faceface with one Fe(1)O6 octahedra. All Ti(1)-O(3) bond lengths are 1.87 Å. All Ti(1)-O(6) bond lengths are 2.10 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to three equivalent O(2) and three equivalent O(5) 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 Fe(1)O6 octahedra. All Mn(1)-O(2) bond lengths are 2.18 Å. All Mn(1)-O(5) bond lengths are 1.99 Å. In the second Mn site, Mn(2) is bonded to three equivalent O(1) and three equivalent O(4) 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 Fe(2)O6 octahedra. All Mn(2)-O(1) bond lengths are 1.98 Å. All Mn(2)-O(4) bond lengths are 2.13 Å. In the third Mn site, Mn(3) is bonded to three equivalent O(7) and three equivalent O(8) atoms to form 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 Fe(2)O6 octahedra. All Mn(3)-O(7) bond lengths are 2.02 Å. All Mn(3)-O(8) bond lengths are 1.93 Å. There are two inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to three equivalent O(2) and three equivalent O(6) atoms to form distorted FeO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one Ti(1)O6 octahedra, and  a faceface with one Mn(1)O6 octahedra. All Fe(1)-O(2) bond lengths are 2.09 Å. All Fe(1)-O(6) bond lengths are 2.13 Å. In the second Fe site, Fe(2) is bonded to three equivalent O(4) and three equivalent O(7) atoms to form distorted FeO6 octahedra that share corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  a faceface with one Mn(2)O6 octahedra, and  a faceface with one Mn(3)O6 octahedra. All Fe(2)-O(4) bond lengths are 2.18 Å. All Fe(2)-O(7) bond lengths are 2.19 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra, and  a cornercorner with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 30-51°. The P(1)-O(1) bond length is 1.51 Å. The P(1)-O(5) bond length is 1.52 Å. The P(1)-O(6) bond length is 1.60 Å. The P(1)-O(7) bond length is 1.57 Å. In the second P site, P(2) is bonded to one O(2), one O(3), one O(4), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Ti(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra,  a cornercorner with one Fe(1)O6 octahedra, and  a cornercorner with one Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-53°. The P(2)-O(2) bond length is 1.57 Å. The P(2)-O(3) bond length is 1.57 Å. The P(2)-O(4) bond length is 1.54 Å. The P(2)-O(8) bond length is 1.52 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to one Mn(1), one Fe(1), and one P(2) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Ti(1) and one P(2) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Mn(2), one Fe(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Ti(1), one Fe(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Mn(3), one Fe(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a bent 150 degrees geometry to one Mn(3) and one P(2) atom.