LiMnPO4 is Chalcostibite-derived structured and crystallizes in the monoclinic P2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(6), and one O(8) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Mn(2)O5 trigonal bipyramids, and corners with two equivalent Mn(1)O4 trigonal pyramids. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(7), and two equivalent O(5) atoms. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(5), one O(7), and one O(8) atom to form MnO4 trigonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. In the second Mn site, Mn(2) is bonded to one O(3), one O(4), one O(6), and two equivalent O(1) atoms to form MnO5 trigonal bipyramids that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and corners with two equivalent Mn(2)O5 trigonal bipyramids. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with two equivalent Mn(2)O5 trigonal bipyramids, and corners with two equivalent Mn(1)O4 trigonal pyramids. In the second P site, P(2) is bonded to one O(1), one O(4), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with three equivalent Mn(2)O5 trigonal bipyramids, and corners with two equivalent Mn(1)O4 trigonal pyramids. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(2), two equivalent Mn(2), and one P(2) 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 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 trigonal non-coplanar geometry to one Li(2), one Mn(2), and one P(2) atom. In the fifth O site, O(5) is bonded to two equivalent Li(2), one Mn(1), and one P(2) atom to form distorted corner-sharing OLi2MnP tetrahedra. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(2) atom.
LiMnPO4 is Chalcostibite-derived structured and crystallizes in the monoclinic P2_1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(2), one O(3), one O(6), and one O(8) atom to form distorted LiO4 tetrahedra that share  a cornercorner with one P(2)O4 tetrahedra, corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Mn(2)O5 trigonal bipyramids, and corners with two equivalent Mn(1)O4 trigonal pyramids. The Li(1)-O(2) bond length is 2.17 Å. The Li(1)-O(3) bond length is 2.11 Å. The Li(1)-O(6) bond length is 2.03 Å. The Li(1)-O(8) bond length is 1.99 Å. In the second Li site, Li(2) is bonded in a 5-coordinate geometry to one O(1), one O(4), one O(7), and two equivalent O(5) atoms. The Li(2)-O(1) bond length is 2.51 Å. The Li(2)-O(4) bond length is 1.99 Å. The Li(2)-O(7) bond length is 1.95 Å. There is one shorter (2.12 Å) and one longer (2.14 Å) Li(2)-O(5) bond length. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(2), one O(5), one O(7), and one O(8) atom to form MnO4 trigonal pyramids that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The Mn(1)-O(2) bond length is 2.04 Å. The Mn(1)-O(5) bond length is 2.09 Å. The Mn(1)-O(7) bond length is 2.10 Å. The Mn(1)-O(8) bond length is 2.12 Å. In the second Mn site, Mn(2) is bonded to one O(3), one O(4), one O(6), and two equivalent O(1) atoms to form MnO5 trigonal bipyramids that share corners with two equivalent Li(1)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and corners with two equivalent Mn(2)O5 trigonal bipyramids. The Mn(2)-O(3) bond length is 2.13 Å. The Mn(2)-O(4) bond length is 2.14 Å. The Mn(2)-O(6) bond length is 2.33 Å. There is one shorter (2.16 Å) and one longer (2.29 Å) Mn(2)-O(1) bond length. There are two inequivalent P sites. In the first P site, P(1) is bonded to one O(2), one O(3), one O(6), and one O(7) atom to form PO4 tetrahedra that share corners with three equivalent Li(1)O4 tetrahedra, corners with two equivalent Mn(2)O5 trigonal bipyramids, and corners with two equivalent Mn(1)O4 trigonal pyramids. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.55 Å. The P(1)-O(6) bond length is 1.55 Å. The P(1)-O(7) bond length is 1.56 Å. In the second P site, P(2) is bonded to one O(1), one O(4), one O(5), and one O(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(1)O4 tetrahedra, corners with three equivalent Mn(2)O5 trigonal bipyramids, and corners with two equivalent Mn(1)O4 trigonal pyramids. The P(2)-O(1) bond length is 1.56 Å. The P(2)-O(4) bond length is 1.54 Å. The P(2)-O(5) bond length is 1.56 Å. The P(2)-O(8) bond length is 1.54 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a 4-coordinate geometry to one Li(2), two equivalent Mn(2), and one P(2) 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 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 trigonal non-coplanar geometry to one Li(2), one Mn(2), and one P(2) atom. In the fifth O site, O(5) is bonded to two equivalent Li(2), one Mn(1), and one P(2) atom to form distorted corner-sharing OLi2MnP tetrahedra. In the sixth O site, O(6) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(2), and one P(1) atom. In the seventh O site, O(7) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(1), and one P(1) atom. In the eighth O site, O(8) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one P(2) atom.