LiMnPO4 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted T-shaped geometry to one O(4), one O(6), and one O(7) atom. In the second Li site, Li(2) is bonded to one O(1), one O(8), and two equivalent O(5) atoms to form LiO4 tetrahedra that share  a cornercorner with one Mn(1)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(4), one O(6), one O(7), and one O(8) atom to form MnO4 tetrahedra that share  a cornercorner with one Li(2)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 in a 5-coordinate geometry to one O(1), one O(3), one O(6), and two equivalent O(2) atoms. 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(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra and corners with two equivalent Mn(1)O4 tetrahedra. In the second P site, P(2) is bonded to one O(1), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O4 tetrahedra and corners with three equivalent Li(2)O4 tetrahedra. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(2), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Mn(2) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(1) atom. 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(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Li(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(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(1), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(2), one Mn(1), and one P(1) atom.
LiMnPO4 crystallizes in the triclinic P-1 space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted T-shaped geometry to one O(4), one O(6), and one O(7) atom. The Li(1)-O(4) bond length is 1.90 Å. The Li(1)-O(6) bond length is 2.05 Å. The Li(1)-O(7) bond length is 1.99 Å. In the second Li site, Li(2) is bonded to one O(1), one O(8), and two equivalent O(5) atoms to form LiO4 tetrahedra that share  a cornercorner with one Mn(1)O4 tetrahedra,  a cornercorner with one P(1)O4 tetrahedra, corners with three equivalent P(2)O4 tetrahedra, and  an edgeedge with one Li(2)O4 tetrahedra. The Li(2)-O(1) bond length is 1.98 Å. The Li(2)-O(8) bond length is 2.22 Å. There is one shorter (1.95 Å) and one longer (2.05 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(4), one O(6), one O(7), and one O(8) atom to form MnO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra, corners with two equivalent P(1)O4 tetrahedra, and corners with two equivalent P(2)O4 tetrahedra. The Mn(1)-O(4) bond length is 2.06 Å. The Mn(1)-O(6) bond length is 2.12 Å. The Mn(1)-O(7) bond length is 2.04 Å. The Mn(1)-O(8) bond length is 2.02 Å. In the second Mn site, Mn(2) is bonded in a 5-coordinate geometry to one O(1), one O(3), one O(6), and two equivalent O(2) atoms. The Mn(2)-O(1) bond length is 2.14 Å. The Mn(2)-O(3) bond length is 2.05 Å. The Mn(2)-O(6) bond length is 2.45 Å. There is one shorter (2.14 Å) and one longer (2.23 Å) Mn(2)-O(2) 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(8) atom to form PO4 tetrahedra that share  a cornercorner with one Li(2)O4 tetrahedra and corners with two equivalent Mn(1)O4 tetrahedra. The P(1)-O(2) bond length is 1.57 Å. The P(1)-O(3) bond length is 1.52 Å. The P(1)-O(6) bond length is 1.59 Å. The P(1)-O(8) bond length is 1.55 Å. In the second P site, P(2) is bonded to one O(1), one O(4), one O(5), and one O(7) atom to form PO4 tetrahedra that share corners with two equivalent Mn(1)O4 tetrahedra and corners with three equivalent Li(2)O4 tetrahedra. The P(2)-O(1) bond length is 1.57 Å. The P(2)-O(4) bond length is 1.58 Å. The P(2)-O(5) bond length is 1.53 Å. The P(2)-O(7) bond length is 1.55 Å. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a distorted trigonal planar geometry to one Li(2), one Mn(2), and one P(2) atom. In the second O site, O(2) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Mn(2) and one P(1) atom. In the third O site, O(3) is bonded in a bent 150 degrees geometry to one Mn(2) and one P(1) atom. 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(2) atom. In the fifth O site, O(5) is bonded in a 3-coordinate geometry to two equivalent Li(2) and one P(2) atom. In the sixth O site, O(6) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Mn(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(1), one Mn(1), and one P(2) atom. In the eighth O site, O(8) is bonded in a distorted T-shaped geometry to one Li(2), one Mn(1), and one P(1) atom.