Li2Mo(PO3)5 crystallizes in the monoclinic P2_1/m space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(8), one O(9), and two equivalent O(3) atoms. Mo(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form MoO6 octahedra that share corners with two equivalent P(3)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Mo(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-53°. In the second P site, P(2) is bonded to one O(8), one O(9), and two equivalent O(6) atoms to form corner-sharing PO4 tetrahedra. In the third P site, P(3) is bonded to one O(1), one O(3), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Mo(1) and one P(3) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Mo(1) and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to two equivalent P(1) atoms. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Mo(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one P(2) and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a trigonal non-coplanar geometry to two equivalent Li(1) and one P(2) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to two equivalent Li(1) and one P(2) atom.
Li2Mo(PO3)5 crystallizes in the monoclinic P2_1/m space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to one O(8), one O(9), and two equivalent O(3) atoms. The Li(1)-O(8) bond length is 2.25 Å. The Li(1)-O(9) bond length is 2.17 Å. There is one shorter (2.03 Å) and one longer (2.52 Å) Li(1)-O(3) bond length. Mo(1) is bonded to two equivalent O(1), two equivalent O(2), and two equivalent O(5) atoms to form MoO6 octahedra that share corners with two equivalent P(3)O4 tetrahedra and corners with four equivalent P(1)O4 tetrahedra. Both Mo(1)-O(1) bond lengths are 2.14 Å. Both Mo(1)-O(2) bond lengths are 2.15 Å. Both Mo(1)-O(5) bond lengths are 2.14 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Mo(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 51-53°. The P(1)-O(2) bond length is 1.51 Å. The P(1)-O(4) bond length is 1.60 Å. The P(1)-O(5) bond length is 1.50 Å. The P(1)-O(7) bond length is 1.60 Å. In the second P site, P(2) is bonded to one O(8), one O(9), and two equivalent O(6) atoms to form corner-sharing PO4 tetrahedra. The P(2)-O(8) bond length is 1.50 Å. The P(2)-O(9) bond length is 1.50 Å. Both P(2)-O(6) bond lengths are 1.64 Å. In the third P site, P(3) is bonded to one O(1), one O(3), one O(6), and one O(7) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, and  a cornercorner with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 49°. The P(3)-O(1) bond length is 1.51 Å. The P(3)-O(3) bond length is 1.49 Å. The P(3)-O(6) bond length is 1.61 Å. The P(3)-O(7) bond length is 1.63 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Mo(1) and one P(3) atom. In the second O site, O(2) is bonded in a distorted bent 120 degrees geometry to one Mo(1) and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to two equivalent Li(1) and one P(3) atom. In the fourth O site, O(4) is bonded in a bent 120 degrees geometry to two equivalent P(1) atoms. In the fifth O site, O(5) is bonded in a distorted bent 120 degrees geometry to one Mo(1) and one P(1) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one P(2) and one P(3) atom. In the seventh O site, O(7) is bonded in a bent 150 degrees geometry to one P(1) and one P(3) atom. In the eighth O site, O(8) is bonded in a trigonal non-coplanar geometry to two equivalent Li(1) and one P(2) atom. In the ninth O site, O(9) is bonded in a trigonal planar geometry to two equivalent Li(1) and one P(2) atom.