LiMn2F5 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with six equivalent Mn(1)F6 octahedra, and edges with four equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 40-60°. Mn(1) is bonded to one F(3), two equivalent F(2), and three equivalent F(1) atoms to form distorted MnF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with four equivalent Mn(1)F6 octahedra,  an edgeedge with one Mn(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, and  a faceface with one Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 40-59°. 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 distorted FLiMn3 trigonal pyramids that share  a cornercorner with one F(3)Li2Mn2 trigonal pyramid, corners with three equivalent F(1)LiMn3 trigonal pyramids, edges with two equivalent F(3)Li2Mn2 trigonal pyramids, and edges with two equivalent F(1)LiMn3 trigonal pyramids. In the second F site, F(2) is bonded in a trigonal planar 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 FLi2Mn2 trigonal pyramids that share corners with two equivalent F(3)Li2Mn2 trigonal pyramids, corners with two equivalent F(1)LiMn3 trigonal pyramids, and edges with four equivalent F(1)LiMn3 trigonal pyramids.
LiMn2F5 crystallizes in the monoclinic C2/c space group. Li(1) is bonded to two equivalent F(1), two equivalent F(2), and two equivalent F(3) atoms to form LiF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with six equivalent Mn(1)F6 octahedra, and edges with four equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 40-60°. Both Li(1)-F(1) bond lengths are 2.09 Å. Both Li(1)-F(2) bond lengths are 2.05 Å. Both Li(1)-F(3) bond lengths are 2.19 Å. Mn(1) is bonded to one F(3), two equivalent F(2), and three equivalent F(1) atoms to form distorted MnF6 octahedra that share corners with three equivalent Li(1)F6 octahedra, corners with four equivalent Mn(1)F6 octahedra,  an edgeedge with one Mn(1)F6 octahedra, edges with two equivalent Li(1)F6 octahedra, and  a faceface with one Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 40-59°. The Mn(1)-F(3) bond length is 2.16 Å. There is one shorter (2.07 Å) and one longer (2.10 Å) Mn(1)-F(2) bond length. There are a spread of Mn(1)-F(1) bond distances ranging from 2.14-2.42 Å. 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 distorted FLiMn3 trigonal pyramids that share  a cornercorner with one F(3)Li2Mn2 trigonal pyramid, corners with three equivalent F(1)LiMn3 trigonal pyramids, edges with two equivalent F(3)Li2Mn2 trigonal pyramids, and edges with two equivalent F(1)LiMn3 trigonal pyramids. In the second F site, F(2) is bonded in a trigonal planar 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 FLi2Mn2 trigonal pyramids that share corners with two equivalent F(3)Li2Mn2 trigonal pyramids, corners with two equivalent F(1)LiMn3 trigonal pyramids, and edges with four equivalent F(1)LiMn3 trigonal pyramids.