LiMn2PO6 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to four equivalent O(1) atoms. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form distorted MnO5 trigonal bipyramids that share corners with two equivalent Mn(2)O5 square pyramids, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one Mn(2)O5 square pyramid. In the second Mn site, Mn(2) is bonded to one O(4), two equivalent O(1), and two equivalent O(2) atoms to form MnO5 square pyramids that share corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Mn(1)O5 trigonal bipyramids, and  an edgeedge with one Mn(1)O5 trigonal bipyramid. P(1) is bonded to one O(3), one O(4), and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with three equivalent Mn(2)O5 square pyramids and corners with three equivalent Mn(1)O5 trigonal bipyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded in a see-saw-like geometry to two equivalent Li(1), one Mn(1), and one Mn(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(1) atom. In the third O site, O(3) is bonded in a linear geometry to one Mn(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Mn(2) and one P(1) atom.
LiMn2PO6 crystallizes in the orthorhombic Pnma space group. Li(1) is bonded in a distorted rectangular see-saw-like geometry to four equivalent O(1) atoms. There are two shorter (1.99 Å) and two longer (2.02 Å) Li(1)-O(1) bond lengths. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(3), two equivalent O(1), and two equivalent O(2) atoms to form distorted MnO5 trigonal bipyramids that share corners with two equivalent Mn(2)O5 square pyramids, corners with three equivalent P(1)O4 tetrahedra, and  an edgeedge with one Mn(2)O5 square pyramid. The Mn(1)-O(3) bond length is 2.04 Å. Both Mn(1)-O(1) bond lengths are 1.84 Å. Both Mn(1)-O(2) bond lengths are 2.05 Å. In the second Mn site, Mn(2) is bonded to one O(4), two equivalent O(1), and two equivalent O(2) atoms to form MnO5 square pyramids that share corners with three equivalent P(1)O4 tetrahedra, corners with two equivalent Mn(1)O5 trigonal bipyramids, and  an edgeedge with one Mn(1)O5 trigonal bipyramid. The Mn(2)-O(4) bond length is 2.01 Å. Both Mn(2)-O(1) bond lengths are 1.84 Å. Both Mn(2)-O(2) bond lengths are 2.04 Å. P(1) is bonded to one O(3), one O(4), and two equivalent O(2) atoms to form PO4 tetrahedra that share corners with three equivalent Mn(2)O5 square pyramids and corners with three equivalent Mn(1)O5 trigonal bipyramids. The P(1)-O(3) bond length is 1.49 Å. The P(1)-O(4) bond length is 1.51 Å. Both P(1)-O(2) bond lengths are 1.58 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a see-saw-like geometry to two equivalent Li(1), one Mn(1), and one Mn(2) atom. In the second O site, O(2) is bonded in a distorted trigonal planar geometry to one Mn(1), one Mn(2), and one P(1) atom. In the third O site, O(3) is bonded in a linear geometry to one Mn(1) and one P(1) atom. In the fourth O site, O(4) is bonded in a distorted bent 120 degrees geometry to one Mn(2) and one P(1) atom.