Tm2P4O13 crystallizes in the orthorhombic C222_1 space group. Tm(1) is bonded to one O(1), one O(4), one O(7), two equivalent O(5), and two equivalent O(6) atoms to form TmO7 pentagonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, edges with two equivalent Tm(1)O7 pentagonal bipyramids, and  an edgeedge with one P(2)O4 tetrahedra. 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 corners with two equivalent Tm(1)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. In the second P site, P(2) is bonded to one O(3), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Tm(1)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra, and  an edgeedge with one Tm(1)O7 pentagonal bipyramid. There are seven inequivalent O sites. In the first O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Tm(1) and one P(2) atom. In the second O site, O(7) is bonded in a bent 150 degrees geometry to one Tm(1) and one P(2) atom. In the third O site, O(1) is bonded in a linear geometry to one Tm(1) and one P(1) atom. In the fourth O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent P(1) atoms. In the fifth O site, O(3) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the sixth O site, O(4) is bonded in a bent 150 degrees geometry to one Tm(1) and one P(1) atom. In the seventh O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Tm(1) and one P(2) atom.
Tm2P4O13 crystallizes in the orthorhombic C222_1 space group. Tm(1) is bonded to one O(1), one O(4), one O(7), two equivalent O(5), and two equivalent O(6) atoms to form TmO7 pentagonal bipyramids that share corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, edges with two equivalent Tm(1)O7 pentagonal bipyramids, and  an edgeedge with one P(2)O4 tetrahedra. The Tm(1)-O(1) bond length is 2.19 Å. The Tm(1)-O(4) bond length is 2.18 Å. The Tm(1)-O(7) bond length is 2.16 Å. There is one shorter (2.31 Å) and one longer (2.48 Å) Tm(1)-O(5) bond length. There is one shorter (2.28 Å) and one longer (2.32 Å) Tm(1)-O(6) bond length. 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 corners with two equivalent Tm(1)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The P(1)-O(1) bond length is 1.48 Å. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.58 Å. The P(1)-O(4) bond length is 1.48 Å. In the second P site, P(2) is bonded to one O(3), one O(5), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Tm(1)O7 pentagonal bipyramids,  a cornercorner with one P(1)O4 tetrahedra, and  an edgeedge with one Tm(1)O7 pentagonal bipyramid. The P(2)-O(3) bond length is 1.61 Å. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.52 Å. The P(2)-O(7) bond length is 1.49 Å. There are seven inequivalent O sites. In the first O site, O(6) is bonded in a 3-coordinate geometry to two equivalent Tm(1) and one P(2) atom. In the second O site, O(7) is bonded in a bent 150 degrees geometry to one Tm(1) and one P(2) atom. In the third O site, O(1) is bonded in a linear geometry to one Tm(1) and one P(1) atom. In the fourth O site, O(2) is bonded in a bent 150 degrees geometry to two equivalent P(1) atoms. In the fifth O site, O(3) is bonded in a bent 120 degrees geometry to one P(1) and one P(2) atom. In the sixth O site, O(4) is bonded in a bent 150 degrees geometry to one Tm(1) and one P(1) atom. In the seventh O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Tm(1) and one P(2) atom.