Li2Mn3F8 crystallizes in the hexagonal P6_3mc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form distorted LiF6 octahedra that share corners with six equivalent Mn(1)F6 octahedra, corners with three equivalent Li(2)F4 tetrahedra, and edges with three equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles are 51°. In the second Li site, Li(2) is bonded to one F(3) and three equivalent F(2) atoms to form LiF4 tetrahedra that share corners with three equivalent Li(1)F6 octahedra and corners with nine equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 53-63°. Mn(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form MnF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)F4 tetrahedra,  an edgeedge with one Li(1)F6 octahedra, and edges with four equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles are 51°. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent Mn(1) atoms. In the third F site, F(3) is bonded in a distorted trigonal pyramidal geometry to one Li(2) and three equivalent Mn(1) atoms. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to three equivalent Mn(1) atoms.
Li2Mn3F8 crystallizes in the hexagonal P6_3mc space group. There are two inequivalent Li sites. In the first Li site, Li(1) is bonded to three equivalent F(1) and three equivalent F(2) atoms to form distorted LiF6 octahedra that share corners with six equivalent Mn(1)F6 octahedra, corners with three equivalent Li(2)F4 tetrahedra, and edges with three equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles are 51°. All Li(1)-F(1) bond lengths are 2.02 Å. All Li(1)-F(2) bond lengths are 2.33 Å. In the second Li site, Li(2) is bonded to one F(3) and three equivalent F(2) atoms to form LiF4 tetrahedra that share corners with three equivalent Li(1)F6 octahedra and corners with nine equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles range from 53-63°. The Li(2)-F(3) bond length is 1.95 Å. All Li(2)-F(2) bond lengths are 2.04 Å. Mn(1) is bonded to one F(3), one F(4), two equivalent F(1), and two equivalent F(2) atoms to form MnF6 octahedra that share corners with two equivalent Li(1)F6 octahedra, corners with three equivalent Li(2)F4 tetrahedra,  an edgeedge with one Li(1)F6 octahedra, and edges with four equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles are 51°. The Mn(1)-F(3) bond length is 2.20 Å. The Mn(1)-F(4) bond length is 2.13 Å. Both Mn(1)-F(1) bond lengths are 2.12 Å. Both Mn(1)-F(2) bond lengths are 2.16 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded in a distorted trigonal planar geometry to one Li(1) and two equivalent Mn(1) atoms. In the second F site, F(2) is bonded in a distorted rectangular see-saw-like geometry to one Li(1), one Li(2), and two equivalent Mn(1) atoms. In the third F site, F(3) is bonded in a distorted trigonal pyramidal geometry to one Li(2) and three equivalent Mn(1) atoms. In the fourth F site, F(4) is bonded in a distorted T-shaped geometry to three equivalent Mn(1) atoms.