Li3Mn3(PO4)4 crystallizes in the monoclinic Pc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(12), one O(5), one O(6), one O(8), and one O(9) atom to form distorted LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Mn(2)O6 pentagonal pyramids,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 62-69°. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(4), one O(6), one O(7), and one O(9) atom to form distorted LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(3)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-69°. In the third Li site, Li(3) is bonded to one O(13), one O(14), one O(16), one O(2), one O(3), and one O(4) atom to form distorted LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Mn(2)O6 pentagonal pyramid,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-75°. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(12), one O(2), one O(3), one O(6), and one O(7) atom to form MnO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-66°. In the second Mn site, Mn(2) is bonded to one O(10), one O(11), one O(13), one O(15), one O(16), and one O(8) atom to form distorted MnO6 pentagonal pyramids that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Mn(3)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Li(3)O6 octahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-69°. In the third Mn site, Mn(3) is bonded to one O(10), one O(11), one O(14), one O(15), one O(16), and one O(5) atom to form distorted MnO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Mn(2)O6 pentagonal pyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-75°. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(14), one O(2), and one O(4) 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 Mn(3)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, and  an edgeedge with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-57°. In the second P site, P(2) is bonded to one O(12), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra,  a cornercorner with one Mn(2)O6 pentagonal pyramid,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-60°. In the third P site, P(3) is bonded to one O(10), one O(11), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(2)O6 pentagonal pyramids,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-60°. In the fourth P site, P(4) is bonded to one O(13), one O(15), one O(16), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra,  a cornercorner with one Mn(2)O6 pentagonal pyramid,  an edgeedge with one Li(3)O6 octahedra, and  an edgeedge with one Mn(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 46-60°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(1), and one P(4) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(2), one 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(1), one Mn(3), and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Mn(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Mn(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(3), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(2), one Mn(3), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(2) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(2), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Li(3), one Mn(3), and one P(1) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Mn(2), one Mn(3), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Mn(2), one Mn(3), and one P(4) atom.
Li3Mn3(PO4)4 crystallizes in the monoclinic Pc space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(11), one O(12), one O(5), one O(6), one O(8), and one O(9) atom to form distorted LiO6 octahedra that share corners with two equivalent Li(2)O6 octahedra, corners with two equivalent Mn(2)O6 pentagonal pyramids,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra,  an edgeedge with one Mn(3)O6 octahedra,  an edgeedge with one P(2)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 62-69°. The Li(1)-O(11) bond length is 2.28 Å. The Li(1)-O(12) bond length is 2.20 Å. The Li(1)-O(5) bond length is 2.24 Å. The Li(1)-O(6) bond length is 2.05 Å. The Li(1)-O(8) bond length is 2.45 Å. The Li(1)-O(9) bond length is 2.07 Å. In the second Li site, Li(2) is bonded to one O(1), one O(2), one O(4), one O(6), one O(7), and one O(9) atom to form distorted LiO6 octahedra that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Mn(1)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra,  an edgeedge with one Li(3)O6 octahedra, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-69°. The Li(2)-O(1) bond length is 2.31 Å. The Li(2)-O(2) bond length is 2.30 Å. The Li(2)-O(4) bond length is 2.03 Å. The Li(2)-O(6) bond length is 2.17 Å. The Li(2)-O(7) bond length is 2.16 Å. The Li(2)-O(9) bond length is 2.02 Å. In the third Li site, Li(3) is bonded to one O(13), one O(14), one O(16), one O(2), one O(3), and one O(4) atom to form distorted LiO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra,  an edgeedge with one Li(2)O6 octahedra,  an edgeedge with one Mn(2)O6 pentagonal pyramid,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-75°. The Li(3)-O(13) bond length is 2.41 Å. The Li(3)-O(14) bond length is 2.31 Å. The Li(3)-O(16) bond length is 2.27 Å. The Li(3)-O(2) bond length is 2.03 Å. The Li(3)-O(3) bond length is 2.17 Å. The Li(3)-O(4) bond length is 1.97 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(12), one O(2), one O(3), one O(6), and one O(7) atom to form MnO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Li(2)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one P(2)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 48-66°. The Mn(1)-O(1) bond length is 1.97 Å. The Mn(1)-O(12) bond length is 2.10 Å. The Mn(1)-O(2) bond length is 2.20 Å. The Mn(1)-O(3) bond length is 2.05 Å. The Mn(1)-O(6) bond length is 2.14 Å. The Mn(1)-O(7) bond length is 2.02 Å. In the second Mn site, Mn(2) is bonded to one O(10), one O(11), one O(13), one O(15), one O(16), and one O(8) atom to form distorted MnO6 pentagonal pyramids that share corners with two equivalent Li(1)O6 octahedra, corners with four equivalent Mn(3)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  a cornercorner with one P(4)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  an edgeedge with one Li(3)O6 octahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 49-69°. The Mn(2)-O(10) bond length is 2.00 Å. The Mn(2)-O(11) bond length is 2.02 Å. The Mn(2)-O(13) bond length is 1.97 Å. The Mn(2)-O(15) bond length is 2.32 Å. The Mn(2)-O(16) bond length is 2.29 Å. The Mn(2)-O(8) bond length is 1.93 Å. In the third Mn site, Mn(3) is bonded to one O(10), one O(11), one O(14), one O(15), one O(16), and one O(5) atom to form distorted MnO6 octahedra that share corners with two equivalent Li(3)O6 octahedra, corners with four equivalent Mn(2)O6 pentagonal pyramids,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(3)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 50-75°. The Mn(3)-O(10) bond length is 2.25 Å. The Mn(3)-O(11) bond length is 2.30 Å. The Mn(3)-O(14) bond length is 1.92 Å. The Mn(3)-O(15) bond length is 2.01 Å. The Mn(3)-O(16) bond length is 2.05 Å. The Mn(3)-O(5) bond length is 1.98 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(14), one O(2), and one O(4) 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 Mn(3)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra,  an edgeedge with one Li(2)O6 octahedra, and  an edgeedge with one Li(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 51-57°. The P(1)-O(1) bond length is 1.58 Å. The P(1)-O(14) bond length is 1.59 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.51 Å. In the second P site, P(2) is bonded to one O(12), one O(6), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Li(2)O6 octahedra,  a cornercorner with one Mn(2)O6 pentagonal pyramid,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 49-60°. The P(2)-O(12) bond length is 1.53 Å. The P(2)-O(6) bond length is 1.56 Å. The P(2)-O(7) bond length is 1.57 Å. The P(2)-O(8) bond length is 1.57 Å. In the third P site, P(3) is bonded to one O(10), one O(11), one O(5), and one O(9) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O6 octahedra,  a cornercorner with one Li(2)O6 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with two equivalent Mn(2)O6 pentagonal pyramids,  an edgeedge with one Li(1)O6 octahedra, and  an edgeedge with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-60°. The P(3)-O(10) bond length is 1.58 Å. The P(3)-O(11) bond length is 1.59 Å. The P(3)-O(5) bond length is 1.55 Å. The P(3)-O(9) bond length is 1.50 Å. In the fourth P site, P(4) is bonded to one O(13), one O(15), one O(16), and one O(3) atom to form PO4 tetrahedra that share  a cornercorner with one Li(3)O6 octahedra,  a cornercorner with one Mn(1)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra,  a cornercorner with one Mn(2)O6 pentagonal pyramid,  an edgeedge with one Li(3)O6 octahedra, and  an edgeedge with one Mn(2)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 46-60°. The P(4)-O(13) bond length is 1.55 Å. The P(4)-O(15) bond length is 1.56 Å. The P(4)-O(16) bond length is 1.58 Å. The P(4)-O(3) bond length is 1.53 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 3-coordinate geometry to one Li(2), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(1), and one P(4) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(2), one 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(1), one Mn(3), and one P(3) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), one Mn(1), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a 3-coordinate geometry to one Li(1), one Mn(2), and one P(2) atom. In the ninth O site, O(9) is bonded in a distorted trigonal planar geometry to one Li(1), one Li(2), and one P(3) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(3), and one P(3) atom. In the eleventh O site, O(11) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(2), one Mn(3), and one P(3) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(2) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(2), and one P(4) atom. In the fourteenth O site, O(14) is bonded in a 3-coordinate geometry to one Li(3), one Mn(3), and one P(1) atom. In the fifteenth O site, O(15) is bonded in a 3-coordinate geometry to one Mn(2), one Mn(3), and one P(4) atom. In the sixteenth O site, O(16) is bonded in a distorted rectangular see-saw-like geometry to one Li(3), one Mn(2), one Mn(3), and one P(4) atom.