Li3Mo2(PO4)3 crystallizes in the trigonal R-3 space group. Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Mo(1)O6 octahedra,  a cornercorner with one Mo(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Mo(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 66-67°. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form MoO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with three equivalent Li(1)O4 tetrahedra. In the second Mo site, Mo(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form MoO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent P(1)O4 tetrahedra. 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, corners with two equivalent Mo(2)O6 octahedra, and corners with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-52°. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Mo(1), and one P(1) atom to form distorted corner-sharing OLi2MoP tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Mo(2), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Mo(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Mo(2) and one P(1) atom.
Li3Mo2(PO4)3 crystallizes in the trigonal R-3 space group. Li(1) is bonded to one O(2), one O(3), and two equivalent O(1) atoms to form distorted LiO4 tetrahedra that share  a cornercorner with one Mo(1)O6 octahedra,  a cornercorner with one Mo(2)O6 octahedra, corners with two equivalent Li(1)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Mo(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 66-67°. The Li(1)-O(2) bond length is 1.96 Å. The Li(1)-O(3) bond length is 1.99 Å. There is one shorter (2.02 Å) and one longer (2.16 Å) Li(1)-O(1) bond length. There are two inequivalent Mo sites. In the first Mo site, Mo(1) is bonded to three equivalent O(1) and three equivalent O(3) atoms to form MoO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with six equivalent P(1)O4 tetrahedra, and edges with three equivalent Li(1)O4 tetrahedra. All Mo(1)-O(1) bond lengths are 2.15 Å. All Mo(1)-O(3) bond lengths are 2.13 Å. In the second Mo site, Mo(2) is bonded to three equivalent O(2) and three equivalent O(4) atoms to form MoO6 octahedra that share corners with three equivalent Li(1)O4 tetrahedra and corners with six equivalent P(1)O4 tetrahedra. All Mo(2)-O(2) bond lengths are 2.17 Å. All Mo(2)-O(4) bond lengths are 2.08 Å. 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, corners with two equivalent Mo(2)O6 octahedra, and corners with four equivalent Li(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 22-52°. The P(1)-O(1) bond length is 1.59 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.51 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Li(1), one Mo(1), and one P(1) atom to form distorted corner-sharing OLi2MoP tetrahedra. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Mo(2), and one P(1) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(1), one Mo(1), and one P(1) atom. In the fourth O site, O(4) is bonded in a bent 150 degrees geometry to one Mo(2) and one P(1) atom.