Li3Mn2(PO4)3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(4) and two equivalent O(6) atoms. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to four equivalent O(2) atoms. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(5) and four equivalent O(4) atoms. Mn(1) is bonded to one O(1), one O(2), one O(5), one O(6), and two equivalent O(3) atoms to form distorted MnO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Mn(1)O6 octahedra. 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 four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-58°. In the second P site, P(2) is bonded to two equivalent O(5) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one P(1) atom. In the second O site, O(2) is bonded to two equivalent Li(2), one Mn(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing OLi2MnP tetrahedra. In the third O site, O(3) is bonded in a 2-coordinate geometry to two equivalent Mn(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Li(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a trigonal non-coplanar geometry to one Li(1), one Mn(1), and one P(2) atom.
Li3Mn2(PO4)3 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to two equivalent O(4) and two equivalent O(6) atoms. Both Li(1)-O(4) bond lengths are 2.14 Å. Both Li(1)-O(6) bond lengths are 2.18 Å. In the second Li site, Li(2) is bonded in a distorted rectangular see-saw-like geometry to four equivalent O(2) atoms. There are two shorter (2.10 Å) and two longer (2.27 Å) Li(2)-O(2) bond lengths. In the third Li site, Li(3) is bonded in a 6-coordinate geometry to two equivalent O(5) and four equivalent O(4) atoms. Both Li(3)-O(5) bond lengths are 2.35 Å. There are two shorter (2.05 Å) and two longer (2.46 Å) Li(3)-O(4) bond lengths. Mn(1) is bonded to one O(1), one O(2), one O(5), one O(6), and two equivalent O(3) atoms to form distorted MnO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Mn(1)O6 octahedra. The Mn(1)-O(1) bond length is 1.89 Å. The Mn(1)-O(2) bond length is 2.19 Å. The Mn(1)-O(5) bond length is 1.95 Å. The Mn(1)-O(6) bond length is 1.96 Å. There is one shorter (1.90 Å) and one longer (2.55 Å) Mn(1)-O(3) 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 four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-58°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.57 Å. The P(1)-O(4) bond length is 1.52 Å. In the second P site, P(2) is bonded to two equivalent O(5) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-54°. Both P(2)-O(5) bond lengths are 1.56 Å. Both P(2)-O(6) bond lengths are 1.56 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a distorted bent 120 degrees geometry to one Mn(1) and one P(1) atom. In the second O site, O(2) is bonded to two equivalent Li(2), one Mn(1), and one P(1) atom to form a mixture of distorted corner and edge-sharing OLi2MnP tetrahedra. In the third O site, O(3) is bonded in a 2-coordinate geometry to two equivalent Mn(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), two equivalent Li(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a trigonal non-coplanar geometry to one Li(1), one Mn(1), and one P(2) atom.