Li2Mn(PO4)2 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted LiO5 trigonal bipyramids that share corners with five equivalent P(1)O4 tetrahedra and  an edgeedge with one Li(1)O5 trigonal bipyramid. Mn(1) is bonded in a distorted square co-planar geometry to two equivalent O(2) and two equivalent O(3) atoms. 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 five equivalent Li(1)O5 trigonal bipyramids. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to two equivalent Li(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(1), and one P(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), 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 Li(1) and one P(1) atom.
Li2Mn(PO4)2 crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(2), one O(3), one O(4), and two equivalent O(1) atoms to form distorted LiO5 trigonal bipyramids that share corners with five equivalent P(1)O4 tetrahedra and  an edgeedge with one Li(1)O5 trigonal bipyramid. The Li(1)-O(2) bond length is 2.47 Å. The Li(1)-O(3) bond length is 2.26 Å. The Li(1)-O(4) bond length is 2.01 Å. There is one shorter (1.96 Å) and one longer (2.03 Å) Li(1)-O(1) bond length. Mn(1) is bonded in a distorted square co-planar geometry to two equivalent O(2) and two equivalent O(3) atoms. Both Mn(1)-O(2) bond lengths are 1.92 Å. Both Mn(1)-O(3) bond lengths are 1.94 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 five equivalent Li(1)O5 trigonal bipyramids. The P(1)-O(1) bond length is 1.52 Å. The P(1)-O(2) bond length is 1.60 Å. The P(1)-O(3) bond length is 1.58 Å. The P(1)-O(4) bond length is 1.53 Å. There are four inequivalent O sites. In the first O site, O(1) is bonded in a distorted T-shaped geometry to two equivalent Li(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(1), and one P(1) atom. In the third O site, O(3) is bonded in a trigonal planar geometry to one Li(1), 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 Li(1) and one P(1) atom.