TmP5 crystallizes in the monoclinic P2_1/m space group. Tm(1) is bonded in a 8-coordinate geometry to two equivalent P(1), two equivalent P(2), and four equivalent P(3) atoms. There are three inequivalent P sites. In the first P site, P(3) is bonded to two equivalent Tm(1), one P(2), and one P(3) atom to form PTm2P2 tetrahedra that share corners with four equivalent P(3)Tm2P2 tetrahedra, corners with five equivalent P(1)Tm2P2 tetrahedra, corners with six equivalent P(2)TmP3 tetrahedra, and  an edgeedge with one P(3)Tm2P2 tetrahedra. In the second P site, P(1) is bonded to two equivalent Tm(1) and two equivalent P(2) atoms to form distorted PTm2P2 tetrahedra that share corners with two equivalent P(1)Tm2P2 tetrahedra, corners with six equivalent P(2)TmP3 tetrahedra, and corners with ten equivalent P(3)Tm2P2 tetrahedra. In the third P site, P(2) is bonded to one Tm(1), one P(1), one P(2), and one P(3) atom to form distorted PTmP3 tetrahedra that share corners with three equivalent P(1)Tm2P2 tetrahedra, corners with six equivalent P(3)Tm2P2 tetrahedra, and  an edgeedge with one P(2)TmP3 tetrahedra.
TmP5 crystallizes in the monoclinic P2_1/m space group. Tm(1) is bonded in a 8-coordinate geometry to two equivalent P(1), two equivalent P(2), and four equivalent P(3) atoms. There is one shorter (2.92 Å) and one longer (3.02 Å) Tm(1)-P(1) bond length. Both Tm(1)-P(2) bond lengths are 2.89 Å. There are two shorter (2.94 Å) and two longer (2.97 Å) Tm(1)-P(3) bond lengths. There are three inequivalent P sites. In the first P site, P(3) is bonded to two equivalent Tm(1), one P(2), and one P(3) atom to form PTm2P2 tetrahedra that share corners with four equivalent P(3)Tm2P2 tetrahedra, corners with five equivalent P(1)Tm2P2 tetrahedra, corners with six equivalent P(2)TmP3 tetrahedra, and  an edgeedge with one P(3)Tm2P2 tetrahedra. The P(3)-P(2) bond length is 2.15 Å. The P(3)-P(3) bond length is 2.20 Å. In the second P site, P(1) is bonded to two equivalent Tm(1) and two equivalent P(2) atoms to form distorted PTm2P2 tetrahedra that share corners with two equivalent P(1)Tm2P2 tetrahedra, corners with six equivalent P(2)TmP3 tetrahedra, and corners with ten equivalent P(3)Tm2P2 tetrahedra. Both P(1)-P(2) bond lengths are 2.19 Å. In the third P site, P(2) is bonded to one Tm(1), one P(1), one P(2), and one P(3) atom to form distorted PTmP3 tetrahedra that share corners with three equivalent P(1)Tm2P2 tetrahedra, corners with six equivalent P(3)Tm2P2 tetrahedra, and  an edgeedge with one P(2)TmP3 tetrahedra. The P(2)-P(2) bond length is 2.18 Å.