LiMn7(O3F)3 is Corundum-derived structured and crystallizes in the trigonal R3 space group. Li(1) is bonded to three equivalent O(3) and three equivalent F(1) atoms to form LiO3F3 octahedra that share corners with three equivalent Mn(2)O4F2 pentagonal pyramids, corners with three equivalent Mn(1)O5F pentagonal pyramids, edges with three equivalent Mn(2)O4F2 pentagonal pyramids, and edges with three equivalent Mn(1)O5F pentagonal pyramids. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), two equivalent O(2), two equivalent O(3), and one F(1) atom to form distorted MnO5F pentagonal pyramids that share  a cornercorner with one Li(1)O3F3 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with four equivalent Mn(1)O5F pentagonal pyramids,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Mn(3)O6 octahedra, and edges with four equivalent Mn(2)O4F2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 39-56°. In the second Mn site, Mn(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent F(1) atoms to form distorted MnO4F2 pentagonal pyramids that share  a cornercorner with one Li(1)O3F3 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with four equivalent Mn(2)O4F2 pentagonal pyramids,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Mn(3)O6 octahedra, and edges with four equivalent Mn(1)O5F pentagonal pyramids. The corner-sharing octahedral tilt angles range from 37-39°. In the third Mn site, Mn(3) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form MnO6 octahedra that share corners with three equivalent Mn(2)O4F2 pentagonal pyramids, corners with three equivalent Mn(1)O5F pentagonal pyramids, edges with three equivalent Mn(2)O4F2 pentagonal pyramids, and edges with three equivalent Mn(1)O5F pentagonal pyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to one Mn(1), one Mn(3), and two equivalent Mn(2) atoms. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Mn(2), one Mn(3), and two equivalent Mn(1) atoms. In the third O site, O(3) is bonded to one Li(1), one Mn(2), and two equivalent Mn(1) atoms to form distorted corner-sharing OLiMn3 trigonal pyramids. F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), and two equivalent Mn(2) atoms.
LiMn7(O3F)3 is Corundum-derived structured and crystallizes in the trigonal R3 space group. Li(1) is bonded to three equivalent O(3) and three equivalent F(1) atoms to form LiO3F3 octahedra that share corners with three equivalent Mn(2)O4F2 pentagonal pyramids, corners with three equivalent Mn(1)O5F pentagonal pyramids, edges with three equivalent Mn(2)O4F2 pentagonal pyramids, and edges with three equivalent Mn(1)O5F pentagonal pyramids. All Li(1)-O(3) bond lengths are 2.11 Å. All Li(1)-F(1) bond lengths are 2.06 Å. There are three inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1), two equivalent O(2), two equivalent O(3), and one F(1) atom to form distorted MnO5F pentagonal pyramids that share  a cornercorner with one Li(1)O3F3 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with four equivalent Mn(1)O5F pentagonal pyramids,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Mn(3)O6 octahedra, and edges with four equivalent Mn(2)O4F2 pentagonal pyramids. The corner-sharing octahedral tilt angles range from 39-56°. The Mn(1)-O(1) bond length is 1.98 Å. There is one shorter (2.03 Å) and one longer (2.32 Å) Mn(1)-O(2) bond length. There is one shorter (1.96 Å) and one longer (2.03 Å) Mn(1)-O(3) bond length. The Mn(1)-F(1) bond length is 2.37 Å. In the second Mn site, Mn(2) is bonded to one O(2), one O(3), two equivalent O(1), and two equivalent F(1) atoms to form distorted MnO4F2 pentagonal pyramids that share  a cornercorner with one Li(1)O3F3 octahedra,  a cornercorner with one Mn(3)O6 octahedra, corners with four equivalent Mn(2)O4F2 pentagonal pyramids,  an edgeedge with one Li(1)O3F3 octahedra,  an edgeedge with one Mn(3)O6 octahedra, and edges with four equivalent Mn(1)O5F pentagonal pyramids. The corner-sharing octahedral tilt angles range from 37-39°. The Mn(2)-O(2) bond length is 2.08 Å. The Mn(2)-O(3) bond length is 2.10 Å. There is one shorter (2.07 Å) and one longer (2.09 Å) Mn(2)-O(1) bond length. There is one shorter (2.10 Å) and one longer (2.16 Å) Mn(2)-F(1) bond length. In the third Mn site, Mn(3) is bonded to three equivalent O(1) and three equivalent O(2) atoms to form MnO6 octahedra that share corners with three equivalent Mn(2)O4F2 pentagonal pyramids, corners with three equivalent Mn(1)O5F pentagonal pyramids, edges with three equivalent Mn(2)O4F2 pentagonal pyramids, and edges with three equivalent Mn(1)O5F pentagonal pyramids. All Mn(3)-O(1) bond lengths are 2.01 Å. All Mn(3)-O(2) bond lengths are 1.95 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded in a distorted see-saw-like geometry to one Mn(1), one Mn(3), and two equivalent Mn(2) atoms. In the second O site, O(2) is bonded in a distorted see-saw-like geometry to one Mn(2), one Mn(3), and two equivalent Mn(1) atoms. In the third O site, O(3) is bonded to one Li(1), one Mn(2), and two equivalent Mn(1) atoms to form distorted corner-sharing OLiMn3 trigonal pyramids. F(1) is bonded in a rectangular see-saw-like geometry to one Li(1), one Mn(1), and two equivalent Mn(2) atoms.