Li2MnF5 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded in a 6-coordinate geometry to one F(3), two equivalent F(1), and three equivalent F(2) atoms. Mn(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form corner-sharing MnF6 octahedra. The corner-sharing octahedral tilt angles are 31°. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(1) and one Mn(1) atom. In the second F site, F(2) is bonded to three equivalent Li(1) and one Mn(1) atom to form distorted FLi3Mn trigonal pyramids that share  a cornercorner with one F(3)Li2Mn2 tetrahedra, corners with three equivalent F(2)Li3Mn trigonal pyramids, edges with two equivalent F(3)Li2Mn2 tetrahedra, and edges with two equivalent F(2)Li3Mn trigonal pyramids. In the third F site, F(3) is bonded to two equivalent Li(1) and two equivalent Mn(1) atoms to form distorted FLi2Mn2 tetrahedra that share corners with two equivalent F(3)Li2Mn2 tetrahedra, corners with two equivalent F(2)Li3Mn trigonal pyramids, and edges with four equivalent F(2)Li3Mn trigonal pyramids.
Li2MnF5 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded in a 6-coordinate geometry to one F(3), two equivalent F(1), and three equivalent F(2) atoms. The Li(1)-F(3) bond length is 2.00 Å. There is one shorter (1.90 Å) and one longer (1.93 Å) Li(1)-F(1) bond length. There are two shorter (2.07 Å) and one longer (2.40 Å) Li(1)-F(2) bond length. Mn(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form corner-sharing MnF6 octahedra. The corner-sharing octahedral tilt angles are 31°. Both Mn(1)-F(1) bond lengths are 1.83 Å. Both Mn(1)-F(2) bond lengths are 1.90 Å. Both Mn(1)-F(3) bond lengths are 2.08 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal non-coplanar geometry to two equivalent Li(1) and one Mn(1) atom. In the second F site, F(2) is bonded to three equivalent Li(1) and one Mn(1) atom to form distorted FLi3Mn trigonal pyramids that share  a cornercorner with one F(3)Li2Mn2 tetrahedra, corners with three equivalent F(2)Li3Mn trigonal pyramids, edges with two equivalent F(3)Li2Mn2 tetrahedra, and edges with two equivalent F(2)Li3Mn trigonal pyramids. In the third F site, F(3) is bonded to two equivalent Li(1) and two equivalent Mn(1) atoms to form distorted FLi2Mn2 tetrahedra that share corners with two equivalent F(3)Li2Mn2 tetrahedra, corners with two equivalent F(2)Li3Mn trigonal pyramids, and edges with four equivalent F(2)Li3Mn trigonal pyramids.