TiMn(PO4)2 crystallizes in the monoclinic P2_1/m space group. Ti(1) is bonded to one O(1), one O(3), two equivalent O(5), and two equivalent O(6) atoms to form distorted TiO6 pentagonal pyramids that share corners with four equivalent Mn(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-51°. Mn(1) is bonded to one O(2), one O(4), two equivalent O(5), and two equivalent O(6) atoms to form distorted MnO6 octahedra that share corners with four equivalent Ti(1)O6 pentagonal pyramids,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), and two equivalent O(5) atoms to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with three equivalent Ti(1)O6 pentagonal pyramids, and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. In the second P site, P(2) is bonded to one O(3), one O(4), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with three equivalent Mn(1)O6 octahedra,  a cornercorner with one Ti(1)O6 pentagonal pyramid, and  an edgeedge with one Ti(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 29-63°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Ti(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Mn(1) and one P(1) 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 bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Ti(1), one Mn(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Ti(1), one Mn(1), and one P(2) atom.
TiMn(PO4)2 crystallizes in the monoclinic P2_1/m space group. Ti(1) is bonded to one O(1), one O(3), two equivalent O(5), and two equivalent O(6) atoms to form distorted TiO6 pentagonal pyramids that share corners with four equivalent Mn(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 46-51°. The Ti(1)-O(1) bond length is 1.89 Å. The Ti(1)-O(3) bond length is 1.90 Å. Both Ti(1)-O(5) bond lengths are 2.04 Å. Both Ti(1)-O(6) bond lengths are 2.06 Å. Mn(1) is bonded to one O(2), one O(4), two equivalent O(5), and two equivalent O(6) atoms to form distorted MnO6 octahedra that share corners with four equivalent Ti(1)O6 pentagonal pyramids,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The Mn(1)-O(2) bond length is 2.06 Å. The Mn(1)-O(4) bond length is 2.07 Å. Both Mn(1)-O(5) bond lengths are 2.35 Å. Both Mn(1)-O(6) bond lengths are 2.24 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), and two equivalent O(5) atoms to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with three equivalent Ti(1)O6 pentagonal pyramids, and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles are 54°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.50 Å. Both P(1)-O(5) bond lengths are 1.58 Å. In the second P site, P(2) is bonded to one O(3), one O(4), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with three equivalent Mn(1)O6 octahedra,  a cornercorner with one Ti(1)O6 pentagonal pyramid, and  an edgeedge with one Ti(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 29-63°. The P(2)-O(3) bond length is 1.55 Å. The P(2)-O(4) bond length is 1.50 Å. Both P(2)-O(6) bond lengths are 1.58 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 150 degrees geometry to one Ti(1) and one P(1) atom. In the second O site, O(2) is bonded in a bent 120 degrees geometry to one Mn(1) and one P(1) 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 bent 150 degrees geometry to one Mn(1) and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Ti(1), one Mn(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Ti(1), one Mn(1), and one P(2) atom.