Li3Mn(PO4)2 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 60-69°. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form distorted LiO6 octahedra that share corners with four equivalent Mn(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-57°. In the third Li site, Li(3) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(8) atoms to form LiO6 octahedra that share corners with four equivalent Mn(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, and edges with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 58-61°. In the fourth Li site, Li(4) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(7) atoms to form LiO6 octahedra that share corners with four equivalent Mn(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-66°. Mn(1) is bonded to one O(2), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form MnO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, corners with four equivalent Li(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-66°. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with three equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-62°. In the second P site, P(2) is bonded to one O(3), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, and  an edgeedge with one Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-56°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one P(2) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), one Mn(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(4), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Mn(1), and one P(2) atom.
Li3Mn(PO4)2 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), one O(5), and one O(6) atom to form LiO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and  an edgeedge with one Li(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 60-69°. The Li(1)-O(1) bond length is 1.98 Å. The Li(1)-O(2) bond length is 2.08 Å. The Li(1)-O(5) bond length is 2.08 Å. The Li(1)-O(6) bond length is 2.23 Å. In the second Li site, Li(2) is bonded to one O(1), one O(3), one O(5), one O(6), one O(7), and one O(8) atom to form distorted LiO6 octahedra that share corners with four equivalent Mn(1)O6 octahedra,  a cornercorner with one Li(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Li(3)O6 octahedra,  an edgeedge with one Li(4)O6 octahedra,  an edgeedge with one Li(1)O4 tetrahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-57°. The Li(2)-O(1) bond length is 2.06 Å. The Li(2)-O(3) bond length is 2.35 Å. The Li(2)-O(5) bond length is 2.09 Å. The Li(2)-O(6) bond length is 2.28 Å. The Li(2)-O(7) bond length is 2.06 Å. The Li(2)-O(8) bond length is 2.20 Å. In the third Li site, Li(3) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(8) atoms to form LiO6 octahedra that share corners with four equivalent Mn(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(4)O6 octahedra, and edges with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 58-61°. Both Li(3)-O(3) bond lengths are 2.07 Å. Both Li(3)-O(4) bond lengths are 2.12 Å. Both Li(3)-O(8) bond lengths are 2.16 Å. In the fourth Li site, Li(4) is bonded to two equivalent O(3), two equivalent O(4), and two equivalent O(7) atoms to form LiO6 octahedra that share corners with four equivalent Mn(1)O6 octahedra, corners with two equivalent P(2)O4 tetrahedra, edges with two equivalent Li(2)O6 octahedra, edges with two equivalent Li(3)O6 octahedra, and edges with two equivalent P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 53-66°. Both Li(4)-O(3) bond lengths are 2.10 Å. Both Li(4)-O(4) bond lengths are 2.13 Å. Both Li(4)-O(7) bond lengths are 2.16 Å. Mn(1) is bonded to one O(2), one O(4), one O(5), one O(6), one O(7), and one O(8) atom to form MnO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with two equivalent Li(4)O6 octahedra, corners with four equivalent Li(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent Li(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 47-66°. The Mn(1)-O(2) bond length is 2.01 Å. The Mn(1)-O(4) bond length is 2.00 Å. The Mn(1)-O(5) bond length is 2.28 Å. The Mn(1)-O(6) bond length is 2.02 Å. The Mn(1)-O(7) bond length is 2.20 Å. The Mn(1)-O(8) bond length is 1.94 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(5), and one O(6) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra, corners with three equivalent Li(2)O6 octahedra, corners with four equivalent Li(1)O4 tetrahedra, and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 39-62°. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.56 Å. The P(1)-O(6) bond length is 1.60 Å. In the second P site, P(2) is bonded to one O(3), one O(4), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Li(4)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Li(3)O6 octahedra, and  an edgeedge with one Li(4)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-56°. The P(2)-O(3) bond length is 1.51 Å. The P(2)-O(4) bond length is 1.59 Å. The P(2)-O(7) bond length is 1.55 Å. The P(2)-O(8) bond length is 1.59 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(1) atom. In the second O site, O(2) is bonded in a trigonal planar geometry to one Li(1), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Li(4), and one P(2) atom. In the fourth O site, O(4) is bonded in a rectangular see-saw-like geometry to one Li(3), one Li(4), one Mn(1), and one P(2) atom. In the fifth O site, O(5) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(1), and one P(1) atom. In the sixth O site, O(6) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), one Mn(1), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(4), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a rectangular see-saw-like geometry to one Li(2), one Li(3), one Mn(1), and one P(2) atom.