LiFe5O5F crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(2), one O(3), and three equivalent F(1) atoms to form LiO2F3 trigonal bipyramids that share  a cornercorner with one Fe(1)O5 trigonal bipyramid,  a cornercorner with one Fe(2)O5 trigonal bipyramid, corners with six equivalent Li(1)O2F3 trigonal bipyramids, edges with three equivalent Fe(4)O4F trigonal bipyramids, and edges with three equivalent Fe(5)O4F trigonal bipyramids. There are five inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(3), and three equivalent O(4) atoms to form FeO5 trigonal bipyramids that share  a cornercorner with one Li(1)O2F3 trigonal bipyramid,  a cornercorner with one Fe(2)O5 trigonal bipyramid, corners with six equivalent Fe(1)O5 trigonal bipyramids, edges with three equivalent Fe(4)O4F trigonal bipyramids, and edges with three equivalent Fe(3)O5 trigonal bipyramids. In the second Fe site, Fe(2) is bonded to one O(1), one O(2), and three equivalent O(5) atoms to form FeO5 trigonal bipyramids that share  a cornercorner with one Li(1)O2F3 trigonal bipyramid,  a cornercorner with one Fe(1)O5 trigonal bipyramid, corners with six equivalent Fe(2)O5 trigonal bipyramids, edges with three equivalent Fe(5)O4F trigonal bipyramids, and edges with three equivalent Fe(3)O5 trigonal bipyramids. In the third Fe site, Fe(3) is bonded to one O(4), one O(5), and three equivalent O(1) atoms to form FeO5 trigonal bipyramids that share  a cornercorner with one Fe(4)O4F trigonal bipyramid,  a cornercorner with one Fe(5)O4F trigonal bipyramid, corners with six equivalent Fe(3)O5 trigonal bipyramids, edges with three equivalent Fe(1)O5 trigonal bipyramids, and edges with three equivalent Fe(2)O5 trigonal bipyramids. In the fourth Fe site, Fe(4) is bonded to one O(4), three equivalent O(3), and one F(1) atom to form FeO4F trigonal bipyramids that share  a cornercorner with one Fe(5)O4F trigonal bipyramid,  a cornercorner with one Fe(3)O5 trigonal bipyramid, corners with six equivalent Fe(4)O4F trigonal bipyramids, edges with three equivalent Li(1)O2F3 trigonal bipyramids, and edges with three equivalent Fe(1)O5 trigonal bipyramids. In the fifth Fe site, Fe(5) is bonded to one O(5), three equivalent O(2), and one F(1) atom to form FeO4F trigonal bipyramids that share  a cornercorner with one Fe(4)O4F trigonal bipyramid,  a cornercorner with one Fe(3)O5 trigonal bipyramid, corners with six equivalent Fe(5)O4F trigonal bipyramids, edges with three equivalent Li(1)O2F3 trigonal bipyramids, and edges with three equivalent Fe(2)O5 trigonal bipyramids. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Fe(1), one Fe(2), and three equivalent Fe(3) atoms to form OFe5 trigonal bipyramids that share  a cornercorner with one O(2)LiFe4 trigonal bipyramid,  a cornercorner with one O(3)LiFe4 trigonal bipyramid, corners with six equivalent O(1)Fe5 trigonal bipyramids, edges with three equivalent O(4)Fe5 trigonal bipyramids, and edges with three equivalent O(5)Fe5 trigonal bipyramids. In the second O site, O(2) is bonded to one Li(1), one Fe(2), and three equivalent Fe(5) atoms to form OLiFe4 trigonal bipyramids that share  a cornercorner with one O(1)Fe5 trigonal bipyramid,  a cornercorner with one O(3)LiFe4 trigonal bipyramid, corners with six equivalent O(2)LiFe4 trigonal bipyramids, edges with three equivalent O(5)Fe5 trigonal bipyramids, and edges with three equivalent F(1)Li3Fe2 trigonal bipyramids. In the third O site, O(3) is bonded to one Li(1), one Fe(1), and three equivalent Fe(4) atoms to form OLiFe4 trigonal bipyramids that share  a cornercorner with one O(1)Fe5 trigonal bipyramid,  a cornercorner with one O(2)LiFe4 trigonal bipyramid, corners with six equivalent O(3)LiFe4 trigonal bipyramids, edges with three equivalent O(4)Fe5 trigonal bipyramids, and edges with three equivalent F(1)Li3Fe2 trigonal bipyramids. In the fourth O site, O(4) is bonded to one Fe(3), one Fe(4), and three equivalent Fe(1) atoms to form OFe5 trigonal bipyramids that share  a cornercorner with one O(5)Fe5 trigonal bipyramid,  a cornercorner with one F(1)Li3Fe2 trigonal bipyramid, corners with six equivalent O(4)Fe5 trigonal bipyramids, edges with three equivalent O(1)Fe5 trigonal bipyramids, and edges with three equivalent O(3)LiFe4 trigonal bipyramids. In the fifth O site, O(5) is bonded to one Fe(3), one Fe(5), and three equivalent Fe(2) atoms to form OFe5 trigonal bipyramids that share  a cornercorner with one O(4)Fe5 trigonal bipyramid,  a cornercorner with one F(1)Li3Fe2 trigonal bipyramid, corners with six equivalent O(5)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), one Fe(4), and one Fe(5) atom to form FLi3Fe2 trigonal bipyramids that share  a cornercorner with one O(4)Fe5 trigonal bipyramid,  a cornercorner with one O(5)Fe5 trigonal bipyramid, corners with six equivalent F(1)Li3Fe2 trigonal bipyramids, edges with three equivalent O(2)LiFe4 trigonal bipyramids, and edges with three equivalent O(3)LiFe4 trigonal bipyramids.
LiFe5O5F crystallizes in the monoclinic Cm space group. Li(1) is bonded to one O(2), one O(3), and three equivalent F(1) atoms to form LiO2F3 trigonal bipyramids that share  a cornercorner with one Fe(1)O5 trigonal bipyramid,  a cornercorner with one Fe(2)O5 trigonal bipyramid, corners with six equivalent Li(1)O2F3 trigonal bipyramids, edges with three equivalent Fe(4)O4F trigonal bipyramids, and edges with three equivalent Fe(5)O4F trigonal bipyramids. The Li(1)-O(2) bond length is 2.21 Å. The Li(1)-O(3) bond length is 2.09 Å. There are two shorter (2.05 Å) and one longer (2.08 Å) Li(1)-F(1) bond length. There are five inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(1), one O(3), and three equivalent O(4) atoms to form FeO5 trigonal bipyramids that share  a cornercorner with one Li(1)O2F3 trigonal bipyramid,  a cornercorner with one Fe(2)O5 trigonal bipyramid, corners with six equivalent Fe(1)O5 trigonal bipyramids, edges with three equivalent Fe(4)O4F trigonal bipyramids, and edges with three equivalent Fe(3)O5 trigonal bipyramids. The Fe(1)-O(1) bond length is 2.24 Å. The Fe(1)-O(3) bond length is 2.31 Å. There are two shorter (2.03 Å) and one longer (2.12 Å) Fe(1)-O(4) bond length. In the second Fe site, Fe(2) is bonded to one O(1), one O(2), and three equivalent O(5) atoms to form FeO5 trigonal bipyramids that share  a cornercorner with one Li(1)O2F3 trigonal bipyramid,  a cornercorner with one Fe(1)O5 trigonal bipyramid, corners with six equivalent Fe(2)O5 trigonal bipyramids, edges with three equivalent Fe(5)O4F trigonal bipyramids, and edges with three equivalent Fe(3)O5 trigonal bipyramids. The Fe(2)-O(1) bond length is 2.28 Å. The Fe(2)-O(2) bond length is 2.28 Å. There are two shorter (2.03 Å) and one longer (2.13 Å) Fe(2)-O(5) bond length. In the third Fe site, Fe(3) is bonded to one O(4), one O(5), and three equivalent O(1) atoms to form FeO5 trigonal bipyramids that share  a cornercorner with one Fe(4)O4F trigonal bipyramid,  a cornercorner with one Fe(5)O4F trigonal bipyramid, corners with six equivalent Fe(3)O5 trigonal bipyramids, edges with three equivalent Fe(1)O5 trigonal bipyramids, and edges with three equivalent Fe(2)O5 trigonal bipyramids. The Fe(3)-O(4) bond length is 2.26 Å. The Fe(3)-O(5) bond length is 2.24 Å. There is one shorter (1.99 Å) and two longer (2.09 Å) Fe(3)-O(1) bond lengths. In the fourth Fe site, Fe(4) is bonded to one O(4), three equivalent O(3), and one F(1) atom to form FeO4F trigonal bipyramids that share  a cornercorner with one Fe(5)O4F trigonal bipyramid,  a cornercorner with one Fe(3)O5 trigonal bipyramid, corners with six equivalent Fe(4)O4F trigonal bipyramids, edges with three equivalent Li(1)O2F3 trigonal bipyramids, and edges with three equivalent Fe(1)O5 trigonal bipyramids. The Fe(4)-O(4) bond length is 2.22 Å. There are two shorter (2.03 Å) and one longer (2.13 Å) Fe(4)-O(3) bond length. The Fe(4)-F(1) bond length is 2.23 Å. In the fifth Fe site, Fe(5) is bonded to one O(5), three equivalent O(2), and one F(1) atom to form FeO4F trigonal bipyramids that share  a cornercorner with one Fe(4)O4F trigonal bipyramid,  a cornercorner with one Fe(3)O5 trigonal bipyramid, corners with six equivalent Fe(5)O4F trigonal bipyramids, edges with three equivalent Li(1)O2F3 trigonal bipyramids, and edges with three equivalent Fe(2)O5 trigonal bipyramids. The Fe(5)-O(5) bond length is 2.25 Å. There is one shorter (1.99 Å) and two longer (2.10 Å) Fe(5)-O(2) bond lengths. The Fe(5)-F(1) bond length is 2.22 Å. There are five inequivalent O sites. In the first O site, O(1) is bonded to one Fe(1), one Fe(2), and three equivalent Fe(3) atoms to form OFe5 trigonal bipyramids that share  a cornercorner with one O(2)LiFe4 trigonal bipyramid,  a cornercorner with one O(3)LiFe4 trigonal bipyramid, corners with six equivalent O(1)Fe5 trigonal bipyramids, edges with three equivalent O(4)Fe5 trigonal bipyramids, and edges with three equivalent O(5)Fe5 trigonal bipyramids. In the second O site, O(2) is bonded to one Li(1), one Fe(2), and three equivalent Fe(5) atoms to form OLiFe4 trigonal bipyramids that share  a cornercorner with one O(1)Fe5 trigonal bipyramid,  a cornercorner with one O(3)LiFe4 trigonal bipyramid, corners with six equivalent O(2)LiFe4 trigonal bipyramids, edges with three equivalent O(5)Fe5 trigonal bipyramids, and edges with three equivalent F(1)Li3Fe2 trigonal bipyramids. In the third O site, O(3) is bonded to one Li(1), one Fe(1), and three equivalent Fe(4) atoms to form OLiFe4 trigonal bipyramids that share  a cornercorner with one O(1)Fe5 trigonal bipyramid,  a cornercorner with one O(2)LiFe4 trigonal bipyramid, corners with six equivalent O(3)LiFe4 trigonal bipyramids, edges with three equivalent O(4)Fe5 trigonal bipyramids, and edges with three equivalent F(1)Li3Fe2 trigonal bipyramids. In the fourth O site, O(4) is bonded to one Fe(3), one Fe(4), and three equivalent Fe(1) atoms to form OFe5 trigonal bipyramids that share  a cornercorner with one O(5)Fe5 trigonal bipyramid,  a cornercorner with one F(1)Li3Fe2 trigonal bipyramid, corners with six equivalent O(4)Fe5 trigonal bipyramids, edges with three equivalent O(1)Fe5 trigonal bipyramids, and edges with three equivalent O(3)LiFe4 trigonal bipyramids. In the fifth O site, O(5) is bonded to one Fe(3), one Fe(5), and three equivalent Fe(2) atoms to form OFe5 trigonal bipyramids that share  a cornercorner with one O(4)Fe5 trigonal bipyramid,  a cornercorner with one F(1)Li3Fe2 trigonal bipyramid, corners with six equivalent O(5)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), one Fe(4), and one Fe(5) atom to form FLi3Fe2 trigonal bipyramids that share  a cornercorner with one O(4)Fe5 trigonal bipyramid,  a cornercorner with one O(5)Fe5 trigonal bipyramid, corners with six equivalent F(1)Li3Fe2 trigonal bipyramids, edges with three equivalent O(2)LiFe4 trigonal bipyramids, and edges with three equivalent O(3)LiFe4 trigonal bipyramids.