Li2MnF4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one F(1) and three equivalent F(2) atoms to form distorted LiF4 tetrahedra that share corners with five equivalent Mn(1)F6 octahedra, corners with four equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 59-80°. Mn(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form MnF6 octahedra that share corners with four equivalent Mn(1)F6 octahedra and corners with ten equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded to three equivalent Li(1) and one Mn(1) atom to form a mixture of distorted corner and edge-sharing FLi3Mn trigonal pyramids.
Li2MnF4 crystallizes in the monoclinic P2_1/c space group. Li(1) is bonded to one F(1) and three equivalent F(2) atoms to form distorted LiF4 tetrahedra that share corners with five equivalent Mn(1)F6 octahedra, corners with four equivalent Li(1)F4 tetrahedra, and  an edgeedge with one Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles range from 59-80°. The Li(1)-F(1) bond length is 1.94 Å. There are a spread of Li(1)-F(2) bond distances ranging from 1.91-1.99 Å. Mn(1) is bonded to two equivalent F(2) and four equivalent F(1) atoms to form MnF6 octahedra that share corners with four equivalent Mn(1)F6 octahedra and corners with ten equivalent Li(1)F4 tetrahedra. The corner-sharing octahedral tilt angles are 53°. Both Mn(1)-F(2) bond lengths are 2.15 Å. There are two shorter (2.14 Å) and two longer (2.17 Å) Mn(1)-F(1) bond lengths. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to one Li(1) and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded to three equivalent Li(1) and one Mn(1) atom to form a mixture of distorted corner and edge-sharing FLi3Mn trigonal pyramids.