LiFe5O5F crystallizes in the orthorhombic Amm2 space group. Li(1) is bonded to two equivalent O(2) and three equivalent F(1) atoms to form LiO2F3 trigonal bipyramids that share corners with two equivalent Fe(1)O5 trigonal bipyramids, corners with six equivalent Li(1)O2F3 trigonal bipyramids, and edges with six equivalent Fe(3)O4F trigonal bipyramids. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), and three equivalent O(3) atoms to form FeO5 trigonal bipyramids that share  a cornercorner with one Li(1)O2F3 trigonal bipyramid, corners with seven equivalent Fe(1)O5 trigonal bipyramids, edges with three equivalent Fe(3)O4F trigonal bipyramids, and edges with three equivalent Fe(2)O5 trigonal bipyramids. In the second Fe site, Fe(2) is bonded to two equivalent O(3) and three equivalent O(1) atoms to form FeO5 trigonal bipyramids that share corners with two equivalent Fe(3)O4F trigonal bipyramids, corners with six equivalent Fe(2)O5 trigonal bipyramids, and edges with six equivalent Fe(1)O5 trigonal bipyramids. In the third Fe site, Fe(3) is bonded to one O(3), three equivalent O(2), and one F(1) atom to form FeO4F trigonal bipyramids that share  a cornercorner with one Fe(2)O5 trigonal bipyramid, corners with seven equivalent Fe(3)O4F trigonal bipyramids, edges with three equivalent Li(1)O2F3 trigonal bipyramids, and edges with three equivalent Fe(1)O5 trigonal bipyramids. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Fe(1) and three equivalent Fe(2) atoms to form OFe5 trigonal bipyramids that share corners with two equivalent O(2)LiFe4 trigonal bipyramids, corners with six equivalent O(1)Fe5 trigonal bipyramids, and edges with six equivalent O(3)Fe5 trigonal bipyramids. In the second O site, O(2) is bonded to one Li(1), one Fe(1), and three equivalent Fe(3) atoms to form OLiFe4 trigonal bipyramids that share  a cornercorner with one O(1)Fe5 trigonal bipyramid, corners with seven equivalent O(2)LiFe4 trigonal bipyramids, edges with three equivalent O(3)Fe5 trigonal bipyramids, and edges with three equivalent F(1)Li3Fe2 trigonal bipyramids. In the third O site, O(3) is bonded to one Fe(2), one Fe(3), and three equivalent Fe(1) atoms to form OFe5 trigonal bipyramids that share  a cornercorner with one F(1)Li3Fe2 trigonal bipyramid, corners with seven equivalent O(3)Fe5 trigonal bipyramids, edges with three equivalent O(1)Fe5 trigonal bipyramids, and edges with three equivalent O(2)LiFe4 trigonal bipyramids. F(1) is bonded to three equivalent Li(1) and two equivalent Fe(3) atoms to form FLi3Fe2 trigonal bipyramids that share corners with two equivalent O(3)Fe5 trigonal bipyramids, corners with six equivalent F(1)Li3Fe2 trigonal bipyramids, and edges with six equivalent O(2)LiFe4 trigonal bipyramids.
LiFe5O5F crystallizes in the orthorhombic Amm2 space group. Li(1) is bonded to two equivalent O(2) and three equivalent F(1) atoms to form LiO2F3 trigonal bipyramids that share corners with two equivalent Fe(1)O5 trigonal bipyramids, corners with six equivalent Li(1)O2F3 trigonal bipyramids, and edges with six equivalent Fe(3)O4F trigonal bipyramids. Both Li(1)-O(2) bond lengths are 2.18 Å. There is one shorter (2.04 Å) and two longer (2.07 Å) Li(1)-F(1) bond lengths. There are three inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(2), and three equivalent O(3) atoms to form FeO5 trigonal bipyramids that share  a cornercorner with one Li(1)O2F3 trigonal bipyramid, corners with seven equivalent Fe(1)O5 trigonal bipyramids, edges with three equivalent Fe(3)O4F trigonal bipyramids, and edges with three equivalent Fe(2)O5 trigonal bipyramids. The Fe(1)-O(1) bond length is 2.28 Å. The Fe(1)-O(2) bond length is 2.27 Å. There is one shorter (2.00 Å) and two longer (2.09 Å) Fe(1)-O(3) bond lengths. In the second Fe site, Fe(2) is bonded to two equivalent O(3) and three equivalent O(1) atoms to form FeO5 trigonal bipyramids that share corners with two equivalent Fe(3)O4F trigonal bipyramids, corners with six equivalent Fe(2)O5 trigonal bipyramids, and edges with six equivalent Fe(1)O5 trigonal bipyramids. Both Fe(2)-O(3) bond lengths are 2.26 Å. There are two shorter (2.02 Å) and one longer (2.14 Å) Fe(2)-O(1) bond length. In the third Fe site, Fe(3) is bonded to one O(3), three equivalent O(2), and one F(1) atom to form FeO4F trigonal bipyramids that share  a cornercorner with one Fe(2)O5 trigonal bipyramid, corners with seven equivalent Fe(3)O4F trigonal bipyramids, edges with three equivalent Li(1)O2F3 trigonal bipyramids, and edges with three equivalent Fe(1)O5 trigonal bipyramids. The Fe(3)-O(3) bond length is 2.23 Å. There are two shorter (2.02 Å) and one longer (2.15 Å) Fe(3)-O(2) bond length. The Fe(3)-F(1) bond length is 2.24 Å. There are three inequivalent O sites. In the first O site, O(1) is bonded to two equivalent Fe(1) and three equivalent Fe(2) atoms to form OFe5 trigonal bipyramids that share corners with two equivalent O(2)LiFe4 trigonal bipyramids, corners with six equivalent O(1)Fe5 trigonal bipyramids, and edges with six equivalent O(3)Fe5 trigonal bipyramids. In the second O site, O(2) is bonded to one Li(1), one Fe(1), and three equivalent Fe(3) atoms to form OLiFe4 trigonal bipyramids that share  a cornercorner with one O(1)Fe5 trigonal bipyramid, corners with seven equivalent O(2)LiFe4 trigonal bipyramids, edges with three equivalent O(3)Fe5 trigonal bipyramids, and edges with three equivalent F(1)Li3Fe2 trigonal bipyramids. In the third O site, O(3) is bonded to one Fe(2), one Fe(3), and three equivalent Fe(1) atoms to form OFe5 trigonal bipyramids that share  a cornercorner with one F(1)Li3Fe2 trigonal bipyramid, corners with seven equivalent O(3)Fe5 trigonal bipyramids, edges with three equivalent O(1)Fe5 trigonal bipyramids, and edges with three equivalent O(2)LiFe4 trigonal bipyramids. F(1) is bonded to three equivalent Li(1) and two equivalent Fe(3) atoms to form FLi3Fe2 trigonal bipyramids that share corners with two equivalent O(3)Fe5 trigonal bipyramids, corners with six equivalent F(1)Li3Fe2 trigonal bipyramids, and edges with six equivalent O(2)LiFe4 trigonal bipyramids.