Li4Mn2(PO4)3 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal non-coplanar geometry to one O(2), one O(5), and one O(7) atom. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(12), one O(3), and one O(4) atom. In the third Li site, Li(3) is bonded to one O(1), one O(11), one O(2), one O(6), and one O(8) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-57°. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one O(10), one O(4), and one O(8) atom. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(11), one O(12), one O(4), one O(5), one O(6), and one O(7) atom to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent Li(3)O5 trigonal bipyramids. In the second Mn site, Mn(2) is bonded to one O(1), one O(10), one O(2), one O(3), one O(8), and one O(9) atom to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(11), one O(4), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 17-53°. In the second P site, P(2) is bonded to one O(3), one O(5), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, and  a cornercorner with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 33-58°. In the third P site, P(3) is bonded to one O(10), one O(12), one O(2), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 37-49°. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Mn(2), and one P(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Mn(2), and one P(3) atom to form distorted edge-sharing OLi2MnP tetrahedra. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(2), one Mn(2), and one P(2) atom. In the fourth O site, O(4) is bonded to one Li(2), one Li(4), one Mn(1), and one P(1) atom to form distorted corner-sharing OLi2MnP trigonal pyramids. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded to one Li(3), one Li(4), one Mn(2), and one P(2) atom to form a mixture of distorted edge and corner-sharing OLi2MnP trigonal pyramids. In the ninth O site, O(9) is bonded in a distorted linear geometry to one Mn(2) and one P(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(4), one Mn(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(3), one Mn(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Mn(1), and one P(3) atom.
Li4Mn2(PO4)3 crystallizes in the triclinic P-1 space group. There are four inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal non-coplanar geometry to one O(2), one O(5), and one O(7) atom. The Li(1)-O(2) bond length is 1.93 Å. The Li(1)-O(5) bond length is 2.05 Å. The Li(1)-O(7) bond length is 1.99 Å. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(1), one O(12), one O(3), and one O(4) atom. The Li(2)-O(1) bond length is 2.06 Å. The Li(2)-O(12) bond length is 2.05 Å. The Li(2)-O(3) bond length is 2.02 Å. The Li(2)-O(4) bond length is 2.23 Å. In the third Li site, Li(3) is bonded to one O(1), one O(11), one O(2), one O(6), and one O(8) atom to form distorted LiO5 trigonal bipyramids that share  a cornercorner with one Mn(2)O6 octahedra, corners with two equivalent Mn(1)O6 octahedra,  a cornercorner with one P(2)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, and  an edgeedge with one P(3)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 43-57°. The Li(3)-O(1) bond length is 2.15 Å. The Li(3)-O(11) bond length is 2.14 Å. The Li(3)-O(2) bond length is 2.26 Å. The Li(3)-O(6) bond length is 2.11 Å. The Li(3)-O(8) bond length is 1.97 Å. In the fourth Li site, Li(4) is bonded in a 3-coordinate geometry to one O(10), one O(4), and one O(8) atom. The Li(4)-O(10) bond length is 1.93 Å. The Li(4)-O(4) bond length is 1.91 Å. The Li(4)-O(8) bond length is 2.01 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(11), one O(12), one O(4), one O(5), one O(6), and one O(7) atom to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra, and corners with two equivalent Li(3)O5 trigonal bipyramids. The Mn(1)-O(11) bond length is 1.94 Å. The Mn(1)-O(12) bond length is 2.00 Å. The Mn(1)-O(4) bond length is 2.29 Å. The Mn(1)-O(5) bond length is 2.24 Å. The Mn(1)-O(6) bond length is 1.96 Å. The Mn(1)-O(7) bond length is 1.99 Å. In the second Mn site, Mn(2) is bonded to one O(1), one O(10), one O(2), one O(3), one O(8), and one O(9) atom to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with two equivalent P(2)O4 tetrahedra, corners with two equivalent P(3)O4 tetrahedra,  a cornercorner with one Li(3)O5 trigonal bipyramid, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The Mn(2)-O(1) bond length is 2.22 Å. The Mn(2)-O(10) bond length is 2.23 Å. The Mn(2)-O(2) bond length is 2.29 Å. The Mn(2)-O(3) bond length is 2.19 Å. The Mn(2)-O(8) bond length is 2.23 Å. The Mn(2)-O(9) bond length is 2.06 Å. There are three inequivalent P sites. In the first P site, P(1) is bonded to one O(1), one O(11), one O(4), and one O(9) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 17-53°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(11) bond length is 1.58 Å. The P(1)-O(4) bond length is 1.56 Å. The P(1)-O(9) bond length is 1.51 Å. In the second P site, P(2) is bonded to one O(3), one O(5), one O(7), and one O(8) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, and  a cornercorner with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 33-58°. The P(2)-O(3) bond length is 1.54 Å. The P(2)-O(5) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.59 Å. The P(2)-O(8) bond length is 1.56 Å. In the third P site, P(3) is bonded to one O(10), one O(12), one O(2), and one O(6) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, and  an edgeedge with one Li(3)O5 trigonal bipyramid. The corner-sharing octahedral tilt angles range from 37-49°. The P(3)-O(10) bond length is 1.54 Å. The P(3)-O(12) bond length is 1.56 Å. The P(3)-O(2) bond length is 1.55 Å. The P(3)-O(6) bond length is 1.57 Å. There are twelve inequivalent O sites. In the first O site, O(1) is bonded in a distorted rectangular see-saw-like geometry to one Li(2), one Li(3), one Mn(2), and one P(1) atom. In the second O site, O(2) is bonded to one Li(1), one Li(3), one Mn(2), and one P(3) atom to form distorted edge-sharing OLi2MnP tetrahedra. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Li(2), one Mn(2), and one P(2) atom. In the fourth O site, O(4) is bonded to one Li(2), one Li(4), one Mn(1), and one P(1) atom to form distorted corner-sharing OLi2MnP trigonal pyramids. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(3), one Mn(1), and one P(3) atom. In the seventh O site, O(7) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded to one Li(3), one Li(4), one Mn(2), and one P(2) atom to form a mixture of distorted edge and corner-sharing OLi2MnP trigonal pyramids. In the ninth O site, O(9) is bonded in a distorted linear geometry to one Mn(2) and one P(1) atom. In the tenth O site, O(10) is bonded in a 3-coordinate geometry to one Li(4), one Mn(2), and one P(3) atom. In the eleventh O site, O(11) is bonded in a 3-coordinate geometry to one Li(3), one Mn(1), and one P(1) atom. In the twelfth O site, O(12) is bonded in a distorted trigonal non-coplanar geometry to one Li(2), one Mn(1), and one P(3) atom.