LiMnPO5 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form distorted LiO6 pentagonal pyramids that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with three 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 range from 28-48°. Mn(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 pentagonal pyramids, corners with four equivalent P(1)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with three equivalent Li(1)O6 pentagonal pyramids. P(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with four equivalent Mn(1)O6 octahedra, corners with two equivalent Li(1)O6 pentagonal pyramids, and  an edgeedge with one Li(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 20-54°. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded to two equivalent Li(1) and two equivalent Mn(1) atoms to form edge-sharing OLi2Mn2 trigonal pyramids. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(1) atom.
LiMnPO5 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form distorted LiO6 pentagonal pyramids that share corners with two equivalent Mn(1)O6 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with three 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 range from 28-48°. The Li(1)-O(1) bond length is 2.29 Å. The Li(1)-O(2) bond length is 2.27 Å. The Li(1)-O(4) bond length is 2.09 Å. The Li(1)-O(5) bond length is 2.20 Å. There is one shorter (2.03 Å) and one longer (2.07 Å) Li(1)-O(3) bond length. Mn(1) is bonded to one O(1), one O(2), one O(4), one O(5), and two equivalent O(3) atoms to form MnO6 octahedra that share corners with two equivalent Li(1)O6 pentagonal pyramids, corners with four equivalent P(1)O4 tetrahedra,  an edgeedge with one Mn(1)O6 octahedra, and edges with three equivalent Li(1)O6 pentagonal pyramids. The Mn(1)-O(1) bond length is 1.92 Å. The Mn(1)-O(2) bond length is 1.98 Å. The Mn(1)-O(4) bond length is 1.95 Å. The Mn(1)-O(5) bond length is 1.97 Å. There is one shorter (1.87 Å) and one longer (1.89 Å) Mn(1)-O(3) bond length. P(1) is bonded to one O(1), one O(2), one O(4), and one O(5) atom to form PO4 tetrahedra that share corners with four equivalent Mn(1)O6 octahedra, corners with two equivalent Li(1)O6 pentagonal pyramids, and  an edgeedge with one Li(1)O6 pentagonal pyramid. The corner-sharing octahedral tilt angles range from 20-54°. The P(1)-O(1) bond length is 1.53 Å. The P(1)-O(2) 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 1.54 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to one Li(1), one Mn(1), and one P(1) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(1) atom. In the third O site, O(3) is bonded to two equivalent Li(1) and two equivalent Mn(1) atoms to form edge-sharing OLi2Mn2 trigonal pyramids. In the fourth O site, O(4) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(1) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to one Li(1), one Mn(1), and one P(1) atom.