Li3Mo3(PO4)4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), one O(5), one O(6), and one O(8) atom. In the second Li site, Li(2) is bonded in a distorted square co-planar geometry to two equivalent O(6) and two equivalent O(8) atoms. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form MoO6 octahedra that share corners with two equivalent Mo(2)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 64°. In the second Mo site, Mo(2) is bonded to one O(1), one O(3), one O(4), one O(6), one O(7), and one O(8) atom to form distorted MoO6 octahedra that share  a cornercorner with one Mo(1)O6 octahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 64°. 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 Mo(1)O6 octahedra and corners with three equivalent Mo(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-60°. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(1)O6 octahedra and corners with three equivalent Mo(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-52°. There are eight inequivalent O sites. In the first O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mo(2), and one P(2) atom. In the second O site, O(7) is bonded in a bent 150 degrees geometry to one Mo(2) and one P(2) atom. In the third O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Mo(2), and one P(2) atom. In the fourth O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Mo(2), and one P(1) atom. In the fifth O site, O(2) is bonded in a bent 150 degrees geometry to one Mo(1) and one P(1) atom. In the sixth O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Mo(2), and one P(1) atom. In the seventh O site, O(4) is bonded in a distorted trigonal planar geometry to one Mo(1), one Mo(2), and one P(1) atom. In the eighth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Mo(1), and one P(2) atom.
Li3Mo3(PO4)4 crystallizes in the monoclinic P2_1/c space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(1), one O(3), one O(5), one O(6), and one O(8) atom. The Li(1)-O(1) bond length is 2.20 Å. The Li(1)-O(3) bond length is 2.01 Å. The Li(1)-O(5) bond length is 1.97 Å. The Li(1)-O(6) bond length is 2.54 Å. The Li(1)-O(8) bond length is 2.04 Å. In the second Li site, Li(2) is bonded in a distorted square co-planar geometry to two equivalent O(6) and two equivalent O(8) atoms. Both Li(2)-O(6) bond lengths are 1.99 Å. Both Li(2)-O(8) bond lengths are 2.12 Å. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to two equivalent O(2), two equivalent O(4), and two equivalent O(5) atoms to form MoO6 octahedra that share corners with two equivalent Mo(2)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 64°. Both Mo(1)-O(2) bond lengths are 2.07 Å. Both Mo(1)-O(4) bond lengths are 2.26 Å. Both Mo(1)-O(5) bond lengths are 2.14 Å. In the second Mo site, Mo(2) is bonded to one O(1), one O(3), one O(4), one O(6), one O(7), and one O(8) atom to form distorted MoO6 octahedra that share  a cornercorner with one Mo(1)O6 octahedra, corners with three equivalent P(1)O4 tetrahedra, and corners with three equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles are 64°. The Mo(2)-O(1) bond length is 2.14 Å. The Mo(2)-O(3) bond length is 2.16 Å. The Mo(2)-O(4) bond length is 2.33 Å. The Mo(2)-O(6) bond length is 2.09 Å. The Mo(2)-O(7) bond length is 2.06 Å. The Mo(2)-O(8) bond length is 2.17 Å. 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 Mo(1)O6 octahedra and corners with three equivalent Mo(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 38-60°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.52 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(4) bond length is 1.59 Å. In the second P site, P(2) is bonded to one O(5), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mo(1)O6 octahedra and corners with three equivalent Mo(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 25-52°. The P(2)-O(5) bond length is 1.56 Å. The P(2)-O(6) bond length is 1.57 Å. The P(2)-O(7) bond length is 1.51 Å. The P(2)-O(8) bond length is 1.56 Å. There are eight inequivalent O sites. In the first O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mo(2), and one P(2) atom. In the second O site, O(7) is bonded in a bent 150 degrees geometry to one Mo(2) and one P(2) atom. In the third O site, O(8) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Mo(2), and one P(2) atom. In the fourth O site, O(1) is bonded in a 3-coordinate geometry to one Li(1), one Mo(2), and one P(1) atom. In the fifth O site, O(2) is bonded in a bent 150 degrees geometry to one Mo(1) and one P(1) atom. In the sixth O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Mo(2), and one P(1) atom. In the seventh O site, O(4) is bonded in a distorted trigonal planar geometry to one Mo(1), one Mo(2), and one P(1) atom. In the eighth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(1), one Mo(1), and one P(2) atom.