Li2Mn5(PO4)4 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 2-coordinate geometry to one O(1), one O(4), and one O(6) atom. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(7) atom to form distorted MnO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, and edges with two equivalent Mn(3)O5 trigonal bipyramids. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Mn(1)O6 octahedra. In the third Mn site, Mn(3) is bonded to one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form MnO5 trigonal bipyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and edges with two equivalent Mn(1)O6 octahedra. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(5), 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, corners with three equivalent Mn(3)O5 trigonal bipyramids, and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. In the second P site, P(2) is bonded to one O(1), one O(2), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra, and corners with two equivalent Mn(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 41-52°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Mn(1), one Mn(2), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Mn(1), one Mn(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one Mn(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one P(2) atom. In the eighth O site, O(8) is bonded in a linear geometry to one Mn(3) and one P(1) atom.
Li2Mn5(PO4)4 crystallizes in the triclinic P-1 space group. Li(1) is bonded in a 2-coordinate geometry to one O(1), one O(4), and one O(6) atom. The Li(1)-O(1) bond length is 2.56 Å. The Li(1)-O(4) bond length is 2.11 Å. The Li(1)-O(6) bond length is 2.25 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(2), one O(3), one O(4), one O(5), and one O(7) atom to form distorted MnO6 octahedra that share  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra,  an edgeedge with one P(1)O4 tetrahedra, and edges with two equivalent Mn(3)O5 trigonal bipyramids. The Mn(1)-O(1) bond length is 2.13 Å. The Mn(1)-O(2) bond length is 2.08 Å. The Mn(1)-O(3) bond length is 2.24 Å. The Mn(1)-O(4) bond length is 2.52 Å. The Mn(1)-O(5) bond length is 2.20 Å. The Mn(1)-O(7) bond length is 2.18 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(1), two equivalent O(3), and two equivalent O(6) atoms to form MnO6 octahedra that share corners with two equivalent P(1)O4 tetrahedra, corners with four equivalent P(2)O4 tetrahedra, and edges with two equivalent Mn(1)O6 octahedra. Both Mn(2)-O(1) bond lengths are 2.30 Å. Both Mn(2)-O(3) bond lengths are 2.16 Å. Both Mn(2)-O(6) bond lengths are 2.18 Å. In the third Mn site, Mn(3) is bonded to one O(2), one O(4), one O(5), one O(7), and one O(8) atom to form MnO5 trigonal bipyramids that share corners with two equivalent P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, and edges with two equivalent Mn(1)O6 octahedra. The Mn(3)-O(2) bond length is 2.20 Å. The Mn(3)-O(4) bond length is 2.20 Å. The Mn(3)-O(5) bond length is 2.17 Å. The Mn(3)-O(7) bond length is 2.19 Å. The Mn(3)-O(8) bond length is 2.02 Å. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(3), one O(4), one O(5), 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, corners with three equivalent Mn(3)O5 trigonal bipyramids, and  an edgeedge with one Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.58 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(2), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent Mn(1)O6 octahedra, and corners with two equivalent Mn(3)O5 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 41-52°. The P(2)-O(1) bond length is 1.57 Å. The P(2)-O(2) bond length is 1.57 Å. The P(2)-O(6) bond length is 1.54 Å. The P(2)-O(7) bond length is 1.55 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(1), one Mn(1), one Mn(2), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one P(2) atom. In the third O site, O(3) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a 4-coordinate geometry to one Li(1), one Mn(1), one Mn(3), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Mn(1), one Mn(3), and one P(1) atom. In the sixth O site, O(6) is bonded in a 3-coordinate geometry to one Li(1), one Mn(2), and one P(2) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one P(2) atom. In the eighth O site, O(8) is bonded in a linear geometry to one Mn(3) and one P(1) atom.