Li2Mn7F16 crystallizes in the trigonal R-3 space group. Li(1) is bonded to one F(4) and three equivalent F(2) atoms to form distorted LiF4 tetrahedra that share corners with three equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles are 68°. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to six equivalent F(2) atoms to form distorted MnF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra. In the second Mn site, Mn(2) is bonded in a 7-coordinate geometry to one F(1), one F(2), one F(4), and four equivalent F(3) atoms. There are four inequivalent F sites. In the first F site, F(4) is bonded to one Li(1) and three equivalent Mn(2) atoms to form a mixture of corner and edge-sharing FLiMn3 tetrahedra. In the second F site, F(1) is bonded in a distorted trigonal planar geometry to three equivalent Mn(2) atoms. In the third F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the fourth F site, F(3) is bonded to four equivalent Mn(2) atoms to form FMn4 tetrahedra that share corners with two equivalent F(4)LiMn3 tetrahedra, corners with six equivalent F(3)Mn4 tetrahedra,  an edgeedge with one F(4)LiMn3 tetrahedra, and edges with three equivalent F(3)Mn4 tetrahedra.
Li2Mn7F16 crystallizes in the trigonal R-3 space group. Li(1) is bonded to one F(4) and three equivalent F(2) atoms to form distorted LiF4 tetrahedra that share corners with three equivalent Mn(1)F6 octahedra. The corner-sharing octahedral tilt angles are 68°. The Li(1)-F(4) bond length is 2.18 Å. All Li(1)-F(2) bond lengths are 2.37 Å. There are two inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to six equivalent F(2) atoms to form distorted MnF6 octahedra that share corners with six equivalent Li(1)F4 tetrahedra. All Mn(1)-F(2) bond lengths are 2.16 Å. In the second Mn site, Mn(2) is bonded in a 7-coordinate geometry to one F(1), one F(2), one F(4), and four equivalent F(3) atoms. The Mn(2)-F(1) bond length is 2.11 Å. The Mn(2)-F(2) bond length is 2.07 Å. The Mn(2)-F(4) bond length is 2.21 Å. There are a spread of Mn(2)-F(3) bond distances ranging from 2.15-2.40 Å. There are four inequivalent F sites. In the first F site, F(4) is bonded to one Li(1) and three equivalent Mn(2) atoms to form a mixture of corner and edge-sharing FLiMn3 tetrahedra. In the second F site, F(1) is bonded in a distorted trigonal planar geometry to three equivalent Mn(2) atoms. In the third F site, F(2) is bonded in a distorted trigonal non-coplanar geometry to one Li(1), one Mn(1), and one Mn(2) atom. In the fourth F site, F(3) is bonded to four equivalent Mn(2) atoms to form FMn4 tetrahedra that share corners with two equivalent F(4)LiMn3 tetrahedra, corners with six equivalent F(3)Mn4 tetrahedra,  an edgeedge with one F(4)LiMn3 tetrahedra, and edges with three equivalent F(3)Mn4 tetrahedra.