LiMn2F5 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. Mn(1) is bonded to one F(3), two equivalent F(2), and three equivalent F(1) atoms to form a mixture of distorted corner and edge-sharing MnF6 octahedra. The corner-sharing octahedral tilt angles range from 29-56°. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1) and three equivalent Mn(1) atoms to form FLiMn3 trigonal pyramids that share  a cornercorner with one F(3)Li2Mn2 tetrahedra, corners with three equivalent F(1)LiMn3 trigonal pyramids, edges with two equivalent F(3)Li2Mn2 tetrahedra, and edges with two equivalent F(1)LiMn3 trigonal pyramids. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1) and two equivalent Mn(1) atoms. 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(1)LiMn3 trigonal pyramids, and edges with four equivalent F(1)LiMn3 trigonal pyramids.
LiMn2F5 crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms. Both Li(1)-F(1) bond lengths are 2.38 Å. Both Li(1)-F(2) bond lengths are 1.91 Å. Both Li(1)-F(3) bond lengths are 2.26 Å. Mn(1) is bonded to one F(3), two equivalent F(2), and three equivalent F(1) atoms to form a mixture of distorted corner and edge-sharing MnF6 octahedra. The corner-sharing octahedral tilt angles range from 29-56°. The Mn(1)-F(3) bond length is 2.15 Å. There is one shorter (2.09 Å) and one longer (2.15 Å) Mn(1)-F(2) bond length. There are two shorter (2.13 Å) and one longer (2.30 Å) Mn(1)-F(1) bond length. There are three inequivalent F sites. In the first F site, F(1) is bonded to one Li(1) and three equivalent Mn(1) atoms to form FLiMn3 trigonal pyramids that share  a cornercorner with one F(3)Li2Mn2 tetrahedra, corners with three equivalent F(1)LiMn3 trigonal pyramids, edges with two equivalent F(3)Li2Mn2 tetrahedra, and edges with two equivalent F(1)LiMn3 trigonal pyramids. In the second F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1) and two equivalent Mn(1) atoms. 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(1)LiMn3 trigonal pyramids, and edges with four equivalent F(1)LiMn3 trigonal pyramids.