LiMn5O5F is Stannite-like structured and crystallizes in the trigonal P3m1 space group. Li(1) is bonded to one O(4) and three equivalent F(1) atoms to form LiOF3 tetrahedra that share corners with three equivalent Mn(3)O3F tetrahedra, corners with three equivalent Mn(2)O4 tetrahedra, and corners with six equivalent Li(1)OF3 tetrahedra. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1) and three equivalent O(3) atoms to form corner-sharing MnO4 tetrahedra. In the second Mn site, Mn(2) is bonded to one O(2) and three equivalent O(4) atoms to form MnO4 tetrahedra that share corners with three equivalent Li(1)OF3 tetrahedra, corners with three equivalent Mn(5)O4 tetrahedra, and corners with six equivalent Mn(2)O4 tetrahedra. In the third Mn site, Mn(3) is bonded to three equivalent O(5) and one F(1) atom to form MnO3F tetrahedra that share corners with three equivalent Li(1)OF3 tetrahedra, corners with three equivalent Mn(4)O4 tetrahedra, and corners with six equivalent Mn(3)O3F tetrahedra. In the fourth Mn site, Mn(4) is bonded to one O(5) and three equivalent O(1) atoms to form MnO4 tetrahedra that share corners with three equivalent Mn(3)O3F tetrahedra, corners with three equivalent Mn(1)O4 tetrahedra, and corners with six equivalent Mn(4)O4 tetrahedra. In the fifth Mn site, Mn(5) is bonded to one O(3) and three equivalent O(2) atoms to form corner-sharing MnO4 tetrahedra. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Mn(1) and three equivalent Mn(4) atoms to form corner-sharing OMn4 tetrahedra. In the second O site, O(2) is bonded to one Mn(2) and three equivalent Mn(5) atoms to form OMn4 tetrahedra that share corners with three equivalent O(4)LiMn3 tetrahedra, corners with three equivalent O(3)Mn4 tetrahedra, and corners with six equivalent O(2)Mn4 tetrahedra. In the third O site, O(3) is bonded to one Mn(5) and three equivalent Mn(1) atoms to form corner-sharing OMn4 tetrahedra. In the fourth O site, O(4) is bonded to one Li(1) and three equivalent Mn(2) atoms to form OLiMn3 tetrahedra that share corners with three equivalent O(2)Mn4 tetrahedra, corners with three equivalent F(1)Li3Mn tetrahedra, and corners with six equivalent O(4)LiMn3 tetrahedra. In the fifth O site, O(5) is bonded to one Mn(4) and three equivalent Mn(3) atoms to form OMn4 tetrahedra that share corners with three equivalent O(1)Mn4 tetrahedra, corners with three equivalent F(1)Li3Mn tetrahedra, and corners with six equivalent O(5)Mn4 tetrahedra. F(1) is bonded to three equivalent Li(1) and one Mn(3) atom to form FLi3Mn tetrahedra that share corners with three equivalent O(4)LiMn3 tetrahedra, corners with three equivalent O(5)Mn4 tetrahedra, and corners with six equivalent F(1)Li3Mn tetrahedra.
LiMn5O5F is Stannite-like structured and crystallizes in the trigonal P3m1 space group. Li(1) is bonded to one O(4) and three equivalent F(1) atoms to form LiOF3 tetrahedra that share corners with three equivalent Mn(3)O3F tetrahedra, corners with three equivalent Mn(2)O4 tetrahedra, and corners with six equivalent Li(1)OF3 tetrahedra. The Li(1)-O(4) bond length is 1.89 Å. All Li(1)-F(1) bond lengths are 2.13 Å. There are five inequivalent Mn sites. In the first Mn site, Mn(1) is bonded to one O(1) and three equivalent O(3) atoms to form corner-sharing MnO4 tetrahedra. The Mn(1)-O(1) bond length is 2.16 Å. All Mn(1)-O(3) bond lengths are 2.08 Å. In the second Mn site, Mn(2) is bonded to one O(2) and three equivalent O(4) atoms to form MnO4 tetrahedra that share corners with three equivalent Li(1)OF3 tetrahedra, corners with three equivalent Mn(5)O4 tetrahedra, and corners with six equivalent Mn(2)O4 tetrahedra. The Mn(2)-O(2) bond length is 2.16 Å. All Mn(2)-O(4) bond lengths are 2.08 Å. In the third Mn site, Mn(3) is bonded to three equivalent O(5) and one F(1) atom to form MnO3F tetrahedra that share corners with three equivalent Li(1)OF3 tetrahedra, corners with three equivalent Mn(4)O4 tetrahedra, and corners with six equivalent Mn(3)O3F tetrahedra. All Mn(3)-O(5) bond lengths are 2.08 Å. The Mn(3)-F(1) bond length is 2.12 Å. In the fourth Mn site, Mn(4) is bonded to one O(5) and three equivalent O(1) atoms to form MnO4 tetrahedra that share corners with three equivalent Mn(3)O3F tetrahedra, corners with three equivalent Mn(1)O4 tetrahedra, and corners with six equivalent Mn(4)O4 tetrahedra. The Mn(4)-O(5) bond length is 2.16 Å. All Mn(4)-O(1) bond lengths are 2.08 Å. In the fifth Mn site, Mn(5) is bonded to one O(3) and three equivalent O(2) atoms to form corner-sharing MnO4 tetrahedra. The Mn(5)-O(3) bond length is 2.16 Å. All Mn(5)-O(2) bond lengths are 2.08 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Mn(1) and three equivalent Mn(4) atoms to form corner-sharing OMn4 tetrahedra. In the second O site, O(2) is bonded to one Mn(2) and three equivalent Mn(5) atoms to form OMn4 tetrahedra that share corners with three equivalent O(4)LiMn3 tetrahedra, corners with three equivalent O(3)Mn4 tetrahedra, and corners with six equivalent O(2)Mn4 tetrahedra. In the third O site, O(3) is bonded to one Mn(5) and three equivalent Mn(1) atoms to form corner-sharing OMn4 tetrahedra. In the fourth O site, O(4) is bonded to one Li(1) and three equivalent Mn(2) atoms to form OLiMn3 tetrahedra that share corners with three equivalent O(2)Mn4 tetrahedra, corners with three equivalent F(1)Li3Mn tetrahedra, and corners with six equivalent O(4)LiMn3 tetrahedra. In the fifth O site, O(5) is bonded to one Mn(4) and three equivalent Mn(3) atoms to form OMn4 tetrahedra that share corners with three equivalent O(1)Mn4 tetrahedra, corners with three equivalent F(1)Li3Mn tetrahedra, and corners with six equivalent O(5)Mn4 tetrahedra. F(1) is bonded to three equivalent Li(1) and one Mn(3) atom to form FLi3Mn tetrahedra that share corners with three equivalent O(4)LiMn3 tetrahedra, corners with three equivalent O(5)Mn4 tetrahedra, and corners with six equivalent F(1)Li3Mn tetrahedra.