LiMnPO5 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form distorted LiO6 pentagonal pyramids that share  a cornercorner with one Mn(2)O6 octahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra,  an edgeedge with one Li(1)O6 pentagonal pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with four equivalent Li(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 40°. In the second Mn site, Mn(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Li(1)O6 pentagonal pyramids, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Li(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 40°. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent Li(1)O6 pentagonal pyramids, and  an edgeedge with one Li(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 32-54°. There are five 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 one Li(1), one Mn(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one Li(1), one Mn(1), and one Mn(2) atom.
LiMnPO5 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(2), one O(3), one O(4), one O(5), and two equivalent O(1) atoms to form distorted LiO6 pentagonal pyramids that share  a cornercorner with one Mn(2)O6 octahedra, corners with three equivalent P(1)O4 tetrahedra,  an edgeedge with one Mn(2)O6 octahedra, edges with two equivalent Mn(1)O6 octahedra,  an edgeedge with one Li(1)O6 pentagonal pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 55°. The Li(1)-O(2) bond length is 2.30 Å. The Li(1)-O(3) bond length is 2.05 Å. The Li(1)-O(4) bond length is 2.35 Å. The Li(1)-O(5) bond length is 1.92 Å. There is one shorter (2.15 Å) and one longer (2.42 Å) Li(1)-O(1) bond length. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Mn(2)O6 octahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with four equivalent Li(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 40°. Both Mn(1)-O(1) bond lengths are 1.97 Å. Both Mn(1)-O(4) bond lengths are 1.94 Å. Both Mn(1)-O(5) bond lengths are 1.85 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent O(5) atoms to form MnO6 octahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Li(1)O6 pentagonal pyramids, corners with four equivalent P(1)O4 tetrahedra, and edges with two equivalent Li(1)O6 pentagonal pyramids. The corner-sharing octahedral tilt angles are 40°. Both Mn(2)-O(2) bond lengths are 1.95 Å. Both Mn(2)-O(3) bond lengths are 1.98 Å. Both Mn(2)-O(5) bond lengths are 1.85 Å. P(1) is bonded to one O(1), one O(2), one O(3), and one O(4) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent Mn(2)O6 octahedra, corners with three equivalent Li(1)O6 pentagonal pyramids, and  an edgeedge with one Li(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 32-54°. The P(1)-O(1) bond length is 1.57 Å. The P(1)-O(2) bond length is 1.55 Å. The P(1)-O(3) bond length is 1.56 Å. The P(1)-O(4) bond length is 1.54 Å. There are five 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 one Li(1), one Mn(2), and one P(1) atom. In the third O site, O(3) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(2), and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted T-shaped geometry to one Li(1), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a trigonal non-coplanar geometry to one Li(1), one Mn(1), and one Mn(2) atom.