LiMn4(PO4)3 crystallizes in the monoclinic C2/c space group. Li(1) is bonded in a square co-planar geometry to four equivalent O(1) atoms. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), one O(4), one O(6), and two equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, and  an edgeedge with one Mn(3)O6 octahedra. In the second Mn site, Mn(2) is bonded in a distorted square co-planar geometry to two equivalent O(4) and two equivalent O(5) atoms. In the third Mn site, Mn(3) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form distorted MnO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four 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(1), one O(2), one O(3), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Mn(3)O6 octahedra and corners with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-56°. In the second P site, P(2) is bonded to two equivalent O(4) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with two equivalent Mn(3)O6 octahedra and corners with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-56°. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Mn(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Mn(2), one Mn(3), and one P(1) 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(2) atom.
LiMn4(PO4)3 crystallizes in the monoclinic C2/c space group. Li(1) is bonded in a square co-planar geometry to four equivalent O(1) atoms. There are two shorter (2.32 Å) and two longer (2.56 Å) Li(1)-O(1) bond lengths. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), one O(3), one O(4), one O(6), and two equivalent O(2) atoms to form MnO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, and  an edgeedge with one Mn(3)O6 octahedra. The Mn(1)-O(1) bond length is 2.21 Å. The Mn(1)-O(3) bond length is 2.19 Å. The Mn(1)-O(4) bond length is 2.09 Å. The Mn(1)-O(6) bond length is 2.14 Å. There is one shorter (2.21 Å) and one longer (2.38 Å) Mn(1)-O(2) bond length. In the second Mn site, Mn(2) is bonded in a distorted square co-planar geometry to two equivalent O(4) and two equivalent O(5) atoms. Both Mn(2)-O(4) bond lengths are 2.11 Å. Both Mn(2)-O(5) bond lengths are 2.03 Å. In the third Mn site, Mn(3) is bonded to two equivalent O(3), two equivalent O(5), and two equivalent O(6) atoms to form distorted MnO6 octahedra that share corners with two equivalent P(2)O4 tetrahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Mn(1)O6 octahedra. Both Mn(3)-O(3) bond lengths are 2.16 Å. Both Mn(3)-O(5) bond lengths are 2.39 Å. Both Mn(3)-O(6) bond lengths are 2.26 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(3), and one O(5) atom to form PO4 tetrahedra that share corners with two equivalent Mn(3)O6 octahedra and corners with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 41-56°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.54 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(5) bond length is 1.59 Å. In the second P site, P(2) is bonded to two equivalent O(4) and two equivalent O(6) atoms to form PO4 tetrahedra that share corners with two equivalent Mn(3)O6 octahedra and corners with four equivalent Mn(1)O6 octahedra. The corner-sharing octahedral tilt angles range from 52-56°. Both P(2)-O(4) bond lengths are 1.57 Å. Both P(2)-O(6) bond lengths are 1.54 Å. There are six inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to two equivalent Li(1), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded in a 3-coordinate geometry to two equivalent Mn(1) and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(3), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Mn(2), one Mn(3), and one P(1) 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(2) atom.