Li3Mn3(PO4)4 crystallizes in the monoclinic C2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one O(12), one O(4), and one O(8) atom. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to two equivalent O(11) and two equivalent O(7) atoms. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(14), one O(4), and one O(8) atom. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(10) atoms. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(10), one O(14), one O(5), one O(6), and one O(9) atom to form MnO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-58°. In the second Mn site, Mn(2) is bonded to one O(11), one O(12), one O(13), one O(2), one O(3), and one O(7) atom to form MnO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-58°. In the third Mn site, Mn(3) is bonded to one O(13), one O(15), one O(16), one O(2), one O(5), and one O(6) atom to form MnO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-58°. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(16), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. In the second P site, P(2) is bonded to one O(1), one O(11), one O(15), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. In the third P site, P(3) is bonded to one O(12), one O(13), one O(2), and one O(3) atom to form PO4 tetrahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra, and  an edgeedge with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. In the fourth P site, P(4) is bonded to one O(14), one O(5), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra, and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-55°. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Mn(1), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(3), and one P(3) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Mn(2) and one P(3) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Li(3), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one P(4) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one P(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(2), one Mn(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(3), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Mn(1) and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(4), one Mn(1), and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(2), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(3), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(1), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one Mn(3) and one P(2) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 150 degrees geometry to one Mn(3) and one P(1) atom.
Li3Mn3(PO4)4 crystallizes in the monoclinic C2 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a 3-coordinate geometry to one O(12), one O(4), and one O(8) atom. The Li(1)-O(12) bond length is 2.25 Å. The Li(1)-O(4) bond length is 1.92 Å. The Li(1)-O(8) bond length is 2.32 Å. In the second Li site, Li(2) is bonded in a rectangular see-saw-like geometry to two equivalent O(11) and two equivalent O(7) atoms. Both Li(2)-O(11) bond lengths are 2.05 Å. Both Li(2)-O(7) bond lengths are 2.20 Å. In the third Li site, Li(3) is bonded in a 4-coordinate geometry to one O(1), one O(14), one O(4), and one O(8) atom. The Li(3)-O(1) bond length is 2.52 Å. The Li(3)-O(14) bond length is 2.20 Å. The Li(3)-O(4) bond length is 2.52 Å. The Li(3)-O(8) bond length is 1.94 Å. In the fourth Li site, Li(4) is bonded in a rectangular see-saw-like geometry to two equivalent O(1) and two equivalent O(10) atoms. Both Li(4)-O(1) bond lengths are 2.21 Å. Both Li(4)-O(10) bond lengths are 2.05 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(10), one O(14), one O(5), one O(6), and one O(9) atom to form MnO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(4)O4 tetrahedra, and  an edgeedge with one P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 55-58°. The Mn(1)-O(1) bond length is 1.96 Å. The Mn(1)-O(10) bond length is 1.99 Å. The Mn(1)-O(14) bond length is 2.24 Å. The Mn(1)-O(5) bond length is 2.01 Å. The Mn(1)-O(6) bond length is 1.98 Å. The Mn(1)-O(9) bond length is 2.17 Å. In the second Mn site, Mn(2) is bonded to one O(11), one O(12), one O(13), one O(2), one O(3), and one O(7) atom to form MnO6 octahedra that share corners with two equivalent Mn(3)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-58°. The Mn(2)-O(11) bond length is 1.99 Å. The Mn(2)-O(12) bond length is 2.23 Å. The Mn(2)-O(13) bond length is 1.98 Å. The Mn(2)-O(2) bond length is 2.01 Å. The Mn(2)-O(3) bond length is 2.18 Å. The Mn(2)-O(7) bond length is 1.96 Å. In the third Mn site, Mn(3) is bonded to one O(13), one O(15), one O(16), one O(2), one O(5), and one O(6) atom to form MnO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra,  a cornercorner with one P(1)O4 tetrahedra,  a cornercorner with one P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent P(4)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-58°. The Mn(3)-O(13) bond length is 1.97 Å. The Mn(3)-O(15) bond length is 1.90 Å. The Mn(3)-O(16) bond length is 1.89 Å. The Mn(3)-O(2) bond length is 2.14 Å. The Mn(3)-O(5) bond length is 2.15 Å. The Mn(3)-O(6) bond length is 1.98 Å. There are four inequivalent P sites. In the first P site, P(1) is bonded to one O(10), one O(16), one O(7), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 44-53°. The P(1)-O(10) bond length is 1.57 Å. The P(1)-O(16) bond length is 1.57 Å. The P(1)-O(7) bond length is 1.57 Å. The P(1)-O(8) bond length is 1.52 Å. In the second P site, P(2) is bonded to one O(1), one O(11), one O(15), and one O(4) atom to form PO4 tetrahedra that share  a cornercorner with one Mn(1)O6 octahedra,  a cornercorner with one Mn(2)O6 octahedra, and  a cornercorner with one Mn(3)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-53°. The P(2)-O(1) bond length is 1.58 Å. The P(2)-O(11) bond length is 1.56 Å. The P(2)-O(15) bond length is 1.57 Å. The P(2)-O(4) bond length is 1.51 Å. In the third P site, P(3) is bonded to one O(12), one O(13), one O(2), and one O(3) atom to form PO4 tetrahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra, and  an edgeedge with one Mn(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 43-55°. The P(3)-O(12) bond length is 1.53 Å. The P(3)-O(13) bond length is 1.63 Å. The P(3)-O(2) bond length is 1.60 Å. The P(3)-O(3) bond length is 1.51 Å. In the fourth P site, P(4) is bonded to one O(14), one O(5), one O(6), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(3)O6 octahedra, and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 42-55°. The P(4)-O(14) bond length is 1.52 Å. The P(4)-O(5) bond length is 1.60 Å. The P(4)-O(6) bond length is 1.63 Å. The P(4)-O(9) bond length is 1.51 Å. There are sixteen inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(3), one Li(4), one Mn(1), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(3), and one P(3) atom. In the third O site, O(3) is bonded in a distorted bent 150 degrees geometry to one Mn(2) and one P(3) atom. In the fourth O site, O(4) is bonded in a 3-coordinate geometry to one Li(1), one Li(3), and one P(2) atom. In the fifth O site, O(5) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one P(4) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one P(4) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(2), one Mn(2), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Li(3), and one P(1) atom. In the ninth O site, O(9) is bonded in a distorted bent 150 degrees geometry to one Mn(1) and one P(4) atom. In the tenth O site, O(10) is bonded in a distorted trigonal planar geometry to one Li(4), one Mn(1), and one P(1) atom. In the eleventh O site, O(11) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(2), and one P(2) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(2), and one P(3) atom. In the thirteenth O site, O(13) is bonded in a distorted trigonal planar geometry to one Mn(2), one Mn(3), and one P(3) atom. In the fourteenth O site, O(14) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(1), and one P(4) atom. In the fifteenth O site, O(15) is bonded in a distorted bent 150 degrees geometry to one Mn(3) and one P(2) atom. In the sixteenth O site, O(16) is bonded in a distorted bent 150 degrees geometry to one Mn(3) and one P(1) atom.