Li3Mn2(PO4)3 crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(8), and two equivalent O(3) atoms. In the second Li site, Li(2) is bonded to one O(2), one O(7), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, and  an edgeedge with one Mn(3)O6 octahedra. In the third Li site, Li(3) is bonded to one O(7), one O(9), and two equivalent O(4) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 68-81°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1) and four equivalent O(6) atoms to form MnO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and edges with two equivalent Mn(2)O6 octahedra. In the second Mn site, Mn(2) is bonded to one O(5), one O(9), two equivalent O(4), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(2)O6 octahedra, and  an edgeedge with one Mn(1)O6 octahedra. In the third Mn site, Mn(3) is bonded to two equivalent O(8) and four equivalent O(3) atoms to form MnO6 octahedra that share corners with six equivalent P(3)O4 tetrahedra and edges with two equivalent Li(2)O6 octahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(9), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-52°. In the second P site, P(2) is bonded to one O(2), one O(5), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-57°. In the third P site, P(3) is bonded to one O(7), one O(8), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Mn(3)O6 octahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-56°. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(2) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Mn(3), and one P(3) atom to form a mixture of distorted corner and edge-sharing OLi2MnP tetrahedra. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Mn(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Mn(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(3), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(2), and one P(1) atom.
Li3Mn2(PO4)3 crystallizes in the monoclinic C2/m space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a 4-coordinate geometry to one O(2), one O(8), and two equivalent O(3) atoms. The Li(1)-O(2) bond length is 1.92 Å. The Li(1)-O(8) bond length is 2.07 Å. Both Li(1)-O(3) bond lengths are 2.09 Å. In the second Li site, Li(2) is bonded to one O(2), one O(7), two equivalent O(3), and two equivalent O(4) atoms to form LiO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, corners with three equivalent P(3)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, and  an edgeedge with one Mn(3)O6 octahedra. The Li(2)-O(2) bond length is 2.03 Å. The Li(2)-O(7) bond length is 2.02 Å. Both Li(2)-O(3) bond lengths are 2.25 Å. Both Li(2)-O(4) bond lengths are 2.28 Å. In the third Li site, Li(3) is bonded to one O(7), one O(9), and two equivalent O(4) atoms to form distorted LiO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 68-81°. The Li(3)-O(7) bond length is 1.95 Å. The Li(3)-O(9) bond length is 2.07 Å. Both Li(3)-O(4) bond lengths are 2.09 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1) and four equivalent O(6) atoms to form MnO6 octahedra that share corners with six equivalent P(1)O4 tetrahedra and edges with two equivalent Mn(2)O6 octahedra. Both Mn(1)-O(1) bond lengths are 1.90 Å. All Mn(1)-O(6) bond lengths are 2.17 Å. In the second Mn site, Mn(2) is bonded to one O(5), one O(9), two equivalent O(4), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with three equivalent Li(3)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(2)O6 octahedra, and  an edgeedge with one Mn(1)O6 octahedra. The Mn(2)-O(5) bond length is 1.88 Å. The Mn(2)-O(9) bond length is 1.95 Å. Both Mn(2)-O(4) bond lengths are 2.11 Å. Both Mn(2)-O(6) bond lengths are 2.21 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(8) and four equivalent O(3) atoms to form MnO6 octahedra that share corners with six equivalent P(3)O4 tetrahedra and edges with two equivalent Li(2)O6 octahedra. Both Mn(3)-O(8) bond lengths are 1.92 Å. All Mn(3)-O(3) bond lengths are 2.13 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(9), and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with three equivalent Mn(1)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 42-52°. The P(1)-O(1) bond length is 1.54 Å. The P(1)-O(9) bond length is 1.56 Å. Both P(1)-O(6) bond lengths are 1.57 Å. In the second P site, P(2) is bonded to one O(2), one O(5), and two equivalent O(4) atoms to form PO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 44-57°. The P(2)-O(2) bond length is 1.51 Å. The P(2)-O(5) bond length is 1.55 Å. Both P(2)-O(4) bond lengths are 1.57 Å. In the third P site, P(3) is bonded to one O(7), one O(8), and two equivalent O(3) atoms to form PO4 tetrahedra that share corners with three equivalent Li(2)O6 octahedra, corners with three equivalent Mn(3)O6 octahedra, and  a cornercorner with one Li(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-56°. The P(3)-O(7) bond length is 1.51 Å. The P(3)-O(8) bond length is 1.58 Å. Both P(3)-O(3) bond lengths are 1.57 Å. There are nine inequivalent O sites. In the first O site, O(1) is bonded in a bent 150 degrees geometry to one Mn(1) and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(2) atom. In the third O site, O(3) is bonded to one Li(1), one Li(2), one Mn(3), and one P(3) atom to form a mixture of distorted corner and edge-sharing OLi2MnP tetrahedra. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(2), one Li(3), one Mn(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted bent 150 degrees geometry to one Mn(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Li(3), and one P(3) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(3), and one P(3) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(2), and one P(1) atom.