LiMnPO4F crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(1), one O(2), two equivalent O(4), and one F(1) atom to form distorted LiO4F square pyramids that share corners with two equivalent Mn(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Mn(1)O4F2 octahedra,  an edgeedge with one Li(1)O4F square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-58°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with two equivalent Mn(2)O4F2 octahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with four equivalent Li(1)O4F square pyramids. The corner-sharing octahedral tilt angles are 51°. In the second Mn site, Mn(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with two equivalent Mn(1)O4F2 octahedra, corners with four equivalent Li(1)O4F square pyramids, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. 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 two equivalent Mn(1)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra, corners with two equivalent Li(1)O4F square pyramids, and  an edgeedge with one Li(1)O4F square pyramid. The corner-sharing octahedral tilt angles range from 34-54°. There are four 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(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 rectangular see-saw-like geometry to two equivalent Li(1), one Mn(1), and one P(1) atom. F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one Mn(2) atom.
LiMnPO4F crystallizes in the triclinic P-1 space group. Li(1) is bonded to one O(1), one O(2), two equivalent O(4), and one F(1) atom to form distorted LiO4F square pyramids that share corners with two equivalent Mn(2)O4F2 octahedra, corners with two equivalent P(1)O4 tetrahedra, edges with two equivalent Mn(1)O4F2 octahedra,  an edgeedge with one Li(1)O4F square pyramid, and  an edgeedge with one P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles range from 54-58°. The Li(1)-O(1) bond length is 2.15 Å. The Li(1)-O(2) bond length is 2.04 Å. There is one shorter (2.16 Å) and one longer (2.28 Å) Li(1)-O(4) bond length. The Li(1)-F(1) bond length is 1.85 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to two equivalent O(1), two equivalent O(4), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with two equivalent Mn(2)O4F2 octahedra, corners with four equivalent P(1)O4 tetrahedra, and edges with four equivalent Li(1)O4F square pyramids. The corner-sharing octahedral tilt angles are 51°. Both Mn(1)-O(1) bond lengths are 1.94 Å. Both Mn(1)-O(4) bond lengths are 2.01 Å. Both Mn(1)-F(1) bond lengths are 2.10 Å. In the second Mn site, Mn(2) is bonded to two equivalent O(2), two equivalent O(3), and two equivalent F(1) atoms to form MnO4F2 octahedra that share corners with two equivalent Mn(1)O4F2 octahedra, corners with four equivalent Li(1)O4F square pyramids, and corners with four equivalent P(1)O4 tetrahedra. The corner-sharing octahedral tilt angles are 51°. Both Mn(2)-O(2) bond lengths are 1.96 Å. Both Mn(2)-O(3) bond lengths are 1.96 Å. Both Mn(2)-F(1) bond lengths are 2.12 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 two equivalent Mn(1)O4F2 octahedra, corners with two equivalent Mn(2)O4F2 octahedra, corners with two equivalent Li(1)O4F square pyramids, and  an edgeedge with one Li(1)O4F square pyramid. The corner-sharing octahedral tilt angles range from 34-54°. The P(1)-O(1) bond length is 1.56 Å. The P(1)-O(2) bond length is 1.56 Å. The P(1)-O(3) bond length is 1.53 Å. The P(1)-O(4) bond length is 1.57 Å. There are four 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(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 rectangular see-saw-like geometry to two equivalent Li(1), one Mn(1), and one P(1) atom. F(1) is bonded in a distorted trigonal planar geometry to one Li(1), one Mn(1), and one Mn(2) atom.