TiMn2P12 crystallizes in the monoclinic C2/c space group. Ti(1) is bonded in a 8-coordinate geometry to two equivalent P(2), two equivalent P(3), two equivalent P(4), and two equivalent P(5) atoms. Mn(1) is bonded to one P(1), one P(3), one P(4), one P(5), and two equivalent P(6) atoms to form MnP6 octahedra that share  a cornercorner with one P(4)TiMnP2 tetrahedra, corners with four equivalent P(2)TiP3 tetrahedra, and  an edgeedge with one Mn(1)P6 octahedra. There are six inequivalent P sites. In the first P site, P(1) is bonded in a distorted single-bond geometry to one Mn(1), one P(1), one P(3), and one P(5) atom. In the second P site, P(2) is bonded to one Ti(1), one P(4), one P(5), and one P(6) atom to form distorted PTiP3 tetrahedra that share corners with four equivalent Mn(1)P6 octahedra,  a cornercorner with one P(2)TiP3 tetrahedra, and corners with three equivalent P(4)TiMnP2 tetrahedra. The corner-sharing octahedral tilt angles range from 54-72°. In the third P site, P(3) is bonded in a 4-coordinate geometry to one Ti(1), one Mn(1), one P(1), and one P(6) atom. In the fourth P site, P(4) is bonded to one Ti(1), one Mn(1), one P(2), and one P(4) atom to form distorted PTiMnP2 tetrahedra that share  a cornercorner with one Mn(1)P6 octahedra,  a cornercorner with one P(4)TiMnP2 tetrahedra, and corners with three equivalent P(2)TiP3 tetrahedra. The corner-sharing octahedral tilt angles are 67°. In the fifth P site, P(5) is bonded in a 4-coordinate geometry to one Ti(1), one Mn(1), one P(1), and one P(2) atom. In the sixth P site, P(6) is bonded in a 4-coordinate geometry to two equivalent Mn(1), one P(2), and one P(3) atom.
TiMn2P12 crystallizes in the monoclinic C2/c space group. Ti(1) is bonded in a 8-coordinate geometry to two equivalent P(2), two equivalent P(3), two equivalent P(4), and two equivalent P(5) atoms. Both Ti(1)-P(2) bond lengths are 2.55 Å. Both Ti(1)-P(3) bond lengths are 2.64 Å. Both Ti(1)-P(4) bond lengths are 2.68 Å. Both Ti(1)-P(5) bond lengths are 2.71 Å. Mn(1) is bonded to one P(1), one P(3), one P(4), one P(5), and two equivalent P(6) atoms to form MnP6 octahedra that share  a cornercorner with one P(4)TiMnP2 tetrahedra, corners with four equivalent P(2)TiP3 tetrahedra, and  an edgeedge with one Mn(1)P6 octahedra. The Mn(1)-P(1) bond length is 2.23 Å. The Mn(1)-P(3) bond length is 2.31 Å. The Mn(1)-P(4) bond length is 2.33 Å. The Mn(1)-P(5) bond length is 2.29 Å. There is one shorter (2.20 Å) and one longer (2.22 Å) Mn(1)-P(6) bond length. There are six inequivalent P sites. In the first P site, P(1) is bonded in a distorted single-bond geometry to one Mn(1), one P(1), one P(3), and one P(5) atom. The P(1)-P(1) bond length is 2.20 Å. The P(1)-P(3) bond length is 2.22 Å. The P(1)-P(5) bond length is 2.24 Å. In the second P site, P(2) is bonded to one Ti(1), one P(4), one P(5), and one P(6) atom to form distorted PTiP3 tetrahedra that share corners with four equivalent Mn(1)P6 octahedra,  a cornercorner with one P(2)TiP3 tetrahedra, and corners with three equivalent P(4)TiMnP2 tetrahedra. The corner-sharing octahedral tilt angles range from 54-72°. The P(2)-P(4) bond length is 2.27 Å. The P(2)-P(5) bond length is 2.31 Å. The P(2)-P(6) bond length is 2.22 Å. In the third P site, P(3) is bonded in a 4-coordinate geometry to one Ti(1), one Mn(1), one P(1), and one P(6) atom. The P(3)-P(6) bond length is 2.21 Å. In the fourth P site, P(4) is bonded to one Ti(1), one Mn(1), one P(2), and one P(4) atom to form distorted PTiMnP2 tetrahedra that share  a cornercorner with one Mn(1)P6 octahedra,  a cornercorner with one P(4)TiMnP2 tetrahedra, and corners with three equivalent P(2)TiP3 tetrahedra. The corner-sharing octahedral tilt angles are 67°. The P(4)-P(4) bond length is 2.28 Å. In the fifth P site, P(5) is bonded in a 4-coordinate geometry to one Ti(1), one Mn(1), one P(1), and one P(2) atom. In the sixth P site, P(6) is bonded in a 4-coordinate geometry to two equivalent Mn(1), one P(2), and one P(3) atom.