Li3Mo(PO3)8 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(8) atoms to form LiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(4), one O(7), and one O(8) atom. Mo(1) is bonded to two equivalent O(10), two equivalent O(11), and two equivalent O(6) atoms to form MoO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(3), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Mo(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-49°. In the second P site, P(2) is bonded to one O(12), one O(6), one O(7), and one O(9) 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(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 32°. In the third P site, P(3) is bonded to one O(1), one O(11), one O(12), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Mo(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-43°. In the fourth P site, P(4) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(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 are 37°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Li(1) and one P(3) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Li(2) and one P(4) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one P(1) and one P(4) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one P(4) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one P(3) and one P(4) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Mo(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a linear geometry to one Li(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Mo(1) and one P(1) atom. In the eleventh O site, O(11) is bonded in a 2-coordinate geometry to one Mo(1) and one P(3) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom.
Li3Mo(PO3)8 crystallizes in the monoclinic C2 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(8) atoms to form LiO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. Both Li(1)-O(1) bond lengths are 2.00 Å. Both Li(1)-O(4) bond lengths are 2.11 Å. Both Li(1)-O(8) bond lengths are 2.16 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to one O(2), one O(4), one O(7), and one O(8) atom. The Li(2)-O(2) bond length is 1.97 Å. The Li(2)-O(4) bond length is 1.93 Å. The Li(2)-O(7) bond length is 2.07 Å. The Li(2)-O(8) bond length is 1.94 Å. Mo(1) is bonded to two equivalent O(10), two equivalent O(11), and two equivalent O(6) atoms to form MoO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with two equivalent P(3)O4 tetrahedra. Both Mo(1)-O(10) bond lengths are 1.98 Å. Both Mo(1)-O(11) bond lengths are 1.99 Å. Both Mo(1)-O(6) bond lengths are 2.04 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(3), one O(8), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Mo(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 20-49°. The P(1)-O(10) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.58 Å. The P(1)-O(8) bond length is 1.47 Å. The P(1)-O(9) bond length is 1.63 Å. In the second P site, P(2) is bonded to one O(12), one O(6), one O(7), and one O(9) 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(3)O4 tetrahedra. The corner-sharing octahedral tilt angles are 32°. The P(2)-O(12) bond length is 1.60 Å. The P(2)-O(6) bond length is 1.55 Å. The P(2)-O(7) bond length is 1.47 Å. The P(2)-O(9) bond length is 1.61 Å. In the third P site, P(3) is bonded to one O(1), one O(11), one O(12), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Mo(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra, and  a cornercorner with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 27-43°. The P(3)-O(1) bond length is 1.46 Å. The P(3)-O(11) bond length is 1.59 Å. The P(3)-O(12) bond length is 1.61 Å. The P(3)-O(5) bond length is 1.57 Å. In the fourth P site, P(4) is bonded to one O(2), one O(3), one O(4), and one O(5) atom to form PO4 tetrahedra that share  a cornercorner with one Li(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 are 37°. The P(4)-O(2) bond length is 1.48 Å. The P(4)-O(3) bond length is 1.67 Å. The P(4)-O(4) bond length is 1.48 Å. The P(4)-O(5) bond length is 1.65 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Li(1) and one P(3) atom. In the second O site, O(2) is bonded in a bent 150 degrees geometry to one Li(2) and one P(4) atom. In the third O site, O(3) is bonded in a bent 120 degrees geometry to one P(1) and one P(4) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Li(2), and one P(4) atom. In the fifth O site, O(5) is bonded in a bent 150 degrees geometry to one P(3) and one P(4) atom. In the sixth O site, O(6) is bonded in a distorted bent 150 degrees geometry to one Mo(1) and one P(2) atom. In the seventh O site, O(7) is bonded in a linear geometry to one Li(2) and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the ninth O site, O(9) is bonded in a bent 150 degrees geometry to one P(1) and one P(2) atom. In the tenth O site, O(10) is bonded in a bent 150 degrees geometry to one Mo(1) and one P(1) atom. In the eleventh O site, O(11) is bonded in a 2-coordinate geometry to one Mo(1) and one P(3) atom. In the twelfth O site, O(12) is bonded in a bent 150 degrees geometry to one P(2) and one P(3) atom.