Li5NiOF5 is Stannite-like structured and crystallizes in the monoclinic Pc space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1) and three equivalent F(4) atoms to form corner-sharing LiF4 tetrahedra. In the second Li site, Li(2) is bonded to one F(2) and three equivalent F(5) atoms to form LiF4 tetrahedra that share corners with three equivalent Li(3)F4 tetrahedra, corners with three equivalent Li(5)OF3 tetrahedra, and corners with six equivalent Li(2)F4 tetrahedra. In the third Li site, Li(3) is bonded to one F(5) and three equivalent F(1) atoms to form corner-sharing LiF4 tetrahedra. In the fourth Li site, Li(4) is bonded to one F(4) and three equivalent F(3) atoms to form LiF4 tetrahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Ni(1)O3F tetrahedra, and corners with six equivalent Li(4)F4 tetrahedra. In the fifth Li site, Li(5) is bonded to one O(1) and three equivalent F(2) atoms to form LiOF3 tetrahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Ni(1)O3F tetrahedra, and corners with six equivalent Li(5)OF3 tetrahedra. Ni(1) is bonded to three equivalent O(1) and one F(3) atom to form NiO3F tetrahedra that share corners with three equivalent Li(4)F4 tetrahedra, corners with three equivalent Li(5)OF3 tetrahedra, and corners with six equivalent Ni(1)O3F tetrahedra. O(1) is bonded to one Li(5) and three equivalent Ni(1) atoms to form OLiNi3 tetrahedra that share corners with three equivalent F(3)Li3Ni tetrahedra, corners with three equivalent F(2)Li4 tetrahedra, and corners with six equivalent O(1)LiNi3 tetrahedra. There are five inequivalent F sites. In the first F site, F(1) is bonded to one Li(1) and three equivalent Li(3) atoms to form corner-sharing FLi4 tetrahedra. In the second F site, F(2) is bonded to one Li(2) and three equivalent Li(5) atoms to form FLi4 tetrahedra that share corners with three equivalent O(1)LiNi3 tetrahedra, corners with three equivalent F(5)Li4 tetrahedra, and corners with six equivalent F(2)Li4 tetrahedra. In the third F site, F(3) is bonded to three equivalent Li(4) and one Ni(1) atom to form FLi3Ni tetrahedra that share corners with three equivalent O(1)LiNi3 tetrahedra, corners with three equivalent F(4)Li4 tetrahedra, and corners with six equivalent F(3)Li3Ni tetrahedra. In the fourth F site, F(4) is bonded to one Li(4) and three equivalent Li(1) atoms to form FLi4 tetrahedra that share corners with three equivalent F(3)Li3Ni tetrahedra, corners with three equivalent F(1)Li4 tetrahedra, and corners with six equivalent F(4)Li4 tetrahedra. In the fifth F site, F(5) is bonded to one Li(3) and three equivalent Li(2) atoms to form corner-sharing FLi4 tetrahedra.
Li5NiOF5 is Stannite-like structured and crystallizes in the monoclinic Pc space group. There are five inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(1) and three equivalent F(4) atoms to form corner-sharing LiF4 tetrahedra. The Li(1)-F(1) bond length is 1.89 Å. All Li(1)-F(4) bond lengths are 1.92 Å. In the second Li site, Li(2) is bonded to one F(2) and three equivalent F(5) atoms to form LiF4 tetrahedra that share corners with three equivalent Li(3)F4 tetrahedra, corners with three equivalent Li(5)OF3 tetrahedra, and corners with six equivalent Li(2)F4 tetrahedra. The Li(2)-F(2) bond length is 1.89 Å. All Li(2)-F(5) bond lengths are 1.92 Å. In the third Li site, Li(3) is bonded to one F(5) and three equivalent F(1) atoms to form corner-sharing LiF4 tetrahedra. The Li(3)-F(5) bond length is 1.90 Å. All Li(3)-F(1) bond lengths are 1.92 Å. In the fourth Li site, Li(4) is bonded to one F(4) and three equivalent F(3) atoms to form LiF4 tetrahedra that share corners with three equivalent Li(1)F4 tetrahedra, corners with three equivalent Ni(1)O3F tetrahedra, and corners with six equivalent Li(4)F4 tetrahedra. The Li(4)-F(4) bond length is 1.89 Å. There is one shorter (1.91 Å) and two longer (1.92 Å) Li(4)-F(3) bond lengths. In the fifth Li site, Li(5) is bonded to one O(1) and three equivalent F(2) atoms to form LiOF3 tetrahedra that share corners with three equivalent Li(2)F4 tetrahedra, corners with three equivalent Ni(1)O3F tetrahedra, and corners with six equivalent Li(5)OF3 tetrahedra. The Li(5)-O(1) bond length is 1.99 Å. All Li(5)-F(2) bond lengths are 1.92 Å. Ni(1) is bonded to three equivalent O(1) and one F(3) atom to form NiO3F tetrahedra that share corners with three equivalent Li(4)F4 tetrahedra, corners with three equivalent Li(5)OF3 tetrahedra, and corners with six equivalent Ni(1)O3F tetrahedra. There is one shorter (1.90 Å) and two longer (1.92 Å) Ni(1)-O(1) bond lengths. The Ni(1)-F(3) bond length is 2.26 Å. O(1) is bonded to one Li(5) and three equivalent Ni(1) atoms to form OLiNi3 tetrahedra that share corners with three equivalent F(3)Li3Ni tetrahedra, corners with three equivalent F(2)Li4 tetrahedra, and corners with six equivalent O(1)LiNi3 tetrahedra. There are five inequivalent F sites. In the first F site, F(1) is bonded to one Li(1) and three equivalent Li(3) atoms to form corner-sharing FLi4 tetrahedra. In the second F site, F(2) is bonded to one Li(2) and three equivalent Li(5) atoms to form FLi4 tetrahedra that share corners with three equivalent O(1)LiNi3 tetrahedra, corners with three equivalent F(5)Li4 tetrahedra, and corners with six equivalent F(2)Li4 tetrahedra. In the third F site, F(3) is bonded to three equivalent Li(4) and one Ni(1) atom to form FLi3Ni tetrahedra that share corners with three equivalent O(1)LiNi3 tetrahedra, corners with three equivalent F(4)Li4 tetrahedra, and corners with six equivalent F(3)Li3Ni tetrahedra. In the fourth F site, F(4) is bonded to one Li(4) and three equivalent Li(1) atoms to form FLi4 tetrahedra that share corners with three equivalent F(3)Li3Ni tetrahedra, corners with three equivalent F(1)Li4 tetrahedra, and corners with six equivalent F(4)Li4 tetrahedra. In the fifth F site, F(5) is bonded to one Li(3) and three equivalent Li(2) atoms to form corner-sharing FLi4 tetrahedra.