LiFe8(OF)8 crystallizes in the triclinic P1 space group. Li(1) is bonded in a 5-coordinate geometry to one O(6), one O(7), two equivalent O(5), and two equivalent O(8) atoms. There are eight inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(3), two equivalent O(2), one F(7), and two equivalent F(8) atoms to form a mixture of corner and edge-sharing FeO3F3 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. In the second Fe site, Fe(2) is bonded to one O(4), one O(7), two equivalent O(1), and two equivalent O(8) atoms to form distorted FeO6 octahedra that share corners with two equivalent Fe(3)O3F3 octahedra, corners with two equivalent Fe(4)O3F3 octahedra, corners with two equivalent Fe(7)O3F3 octahedra, corners with two equivalent Fe(8)O3F3 octahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. In the third Fe site, Fe(3) is bonded to one O(1), two equivalent O(3), one F(3), and two equivalent F(1) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(6)F6 octahedra, corners with two equivalent Fe(1)O3F3 octahedra, corners with two equivalent Fe(5)O3F3 octahedra, corners with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. In the fourth Fe site, Fe(4) is bonded to one O(2), two equivalent O(4), one F(4), and two equivalent F(2) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(6)F6 octahedra, corners with two equivalent Fe(1)O3F3 octahedra, corners with two equivalent Fe(5)O3F3 octahedra, corners with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. In the fifth Fe site, Fe(5) is bonded to one O(6), two equivalent O(5), one F(1), and two equivalent F(4) atoms to form a mixture of corner and edge-sharing FeO3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. In the sixth Fe site, Fe(6) is bonded to one F(2), one F(6), two equivalent F(3), and two equivalent F(5) atoms to form FeF6 octahedra that share corners with two equivalent Fe(3)O3F3 octahedra, corners with two equivalent Fe(4)O3F3 octahedra, corners with two equivalent Fe(7)O3F3 octahedra, corners with two equivalent Fe(8)O3F3 octahedra, and edges with two equivalent Fe(6)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-49°. In the seventh Fe site, Fe(7) is bonded to one O(5), two equivalent O(7), one F(8), and two equivalent F(6) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(6)F6 octahedra, corners with two equivalent Fe(1)O3F3 octahedra, corners with two equivalent Fe(5)O3F3 octahedra, corners with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(7)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. In the eighth Fe site, Fe(8) is bonded to one O(8), two equivalent O(6), one F(5), and two equivalent F(7) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(6)F6 octahedra, corners with two equivalent Fe(1)O3F3 octahedra, corners with two equivalent Fe(5)O3F3 octahedra, corners with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(8)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Fe(3) and two equivalent Fe(2) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one Fe(4) and two equivalent Fe(1) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Fe(1) and two equivalent Fe(3) atoms. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Fe(2) and two equivalent Fe(4) atoms. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to two equivalent Li(1), one Fe(7), and two equivalent Fe(5) atoms. In the sixth O site, O(6) is bonded to one Li(1), one Fe(5), and two equivalent Fe(8) atoms to form corner-sharing OLiFe3 trigonal pyramids. In the seventh O site, O(7) is bonded to one Li(1), one Fe(2), and two equivalent Fe(7) atoms to form distorted corner-sharing OLiFe3 trigonal pyramids. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to two equivalent Li(1), one Fe(8), and two equivalent Fe(2) atoms. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Fe(5) and two equivalent Fe(3) atoms. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Fe(6) and two equivalent Fe(4) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Fe(3) and two equivalent Fe(6) atoms. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Fe(4) and two equivalent Fe(5) atoms. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Fe(8) and two equivalent Fe(6) atoms. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Fe(6) and two equivalent Fe(7) atoms. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Fe(1) and two equivalent Fe(8) atoms. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one Fe(7) and two equivalent Fe(1) atoms.
LiFe8(OF)8 crystallizes in the triclinic P1 space group. Li(1) is bonded in a 5-coordinate geometry to one O(6), one O(7), two equivalent O(5), and two equivalent O(8) atoms. The Li(1)-O(6) bond length is 1.89 Å. The Li(1)-O(7) bond length is 1.86 Å. There is one shorter (2.19 Å) and one longer (2.51 Å) Li(1)-O(5) bond length. There is one shorter (1.96 Å) and one longer (2.20 Å) Li(1)-O(8) bond length. There are eight inequivalent Fe sites. In the first Fe site, Fe(1) is bonded to one O(3), two equivalent O(2), one F(7), and two equivalent F(8) atoms to form a mixture of corner and edge-sharing FeO3F3 octahedra. The corner-sharing octahedral tilt angles range from 47-53°. The Fe(1)-O(3) bond length is 1.94 Å. Both Fe(1)-O(2) bond lengths are 1.93 Å. The Fe(1)-F(7) bond length is 2.20 Å. There is one shorter (2.14 Å) and one longer (2.15 Å) Fe(1)-F(8) bond length. In the second Fe site, Fe(2) is bonded to one O(4), one O(7), two equivalent O(1), and two equivalent O(8) atoms to form distorted FeO6 octahedra that share corners with two equivalent Fe(3)O3F3 octahedra, corners with two equivalent Fe(4)O3F3 octahedra, corners with two equivalent Fe(7)O3F3 octahedra, corners with two equivalent Fe(8)O3F3 octahedra, and edges with two equivalent Fe(2)O6 octahedra. The corner-sharing octahedral tilt angles range from 45-55°. The Fe(2)-O(4) bond length is 1.98 Å. The Fe(2)-O(7) bond length is 2.21 Å. There is one shorter (1.96 Å) and one longer (1.97 Å) Fe(2)-O(1) bond length. There is one shorter (2.12 Å) and one longer (2.23 Å) Fe(2)-O(8) bond length. In the third Fe site, Fe(3) is bonded to one O(1), two equivalent O(3), one F(3), and two equivalent F(1) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(6)F6 octahedra, corners with two equivalent Fe(1)O3F3 octahedra, corners with two equivalent Fe(5)O3F3 octahedra, corners with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(3)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-53°. The Fe(3)-O(1) bond length is 1.90 Å. Both Fe(3)-O(3) bond lengths are 1.94 Å. The Fe(3)-F(3) bond length is 2.11 Å. Both Fe(3)-F(1) bond lengths are 2.18 Å. In the fourth Fe site, Fe(4) is bonded to one O(2), two equivalent O(4), one F(4), and two equivalent F(2) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(6)F6 octahedra, corners with two equivalent Fe(1)O3F3 octahedra, corners with two equivalent Fe(5)O3F3 octahedra, corners with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(4)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. The Fe(4)-O(2) bond length is 1.95 Å. Both Fe(4)-O(4) bond lengths are 1.91 Å. The Fe(4)-F(4) bond length is 2.23 Å. There is one shorter (2.16 Å) and one longer (2.17 Å) Fe(4)-F(2) bond length. In the fifth Fe site, Fe(5) is bonded to one O(6), two equivalent O(5), one F(1), and two equivalent F(4) atoms to form a mixture of corner and edge-sharing FeO3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. The Fe(5)-O(6) bond length is 2.02 Å. Both Fe(5)-O(5) bond lengths are 2.00 Å. The Fe(5)-F(1) bond length is 2.06 Å. There is one shorter (2.07 Å) and one longer (2.09 Å) Fe(5)-F(4) bond length. In the sixth Fe site, Fe(6) is bonded to one F(2), one F(6), two equivalent F(3), and two equivalent F(5) atoms to form FeF6 octahedra that share corners with two equivalent Fe(3)O3F3 octahedra, corners with two equivalent Fe(4)O3F3 octahedra, corners with two equivalent Fe(7)O3F3 octahedra, corners with two equivalent Fe(8)O3F3 octahedra, and edges with two equivalent Fe(6)F6 octahedra. The corner-sharing octahedral tilt angles range from 46-49°. The Fe(6)-F(2) bond length is 2.08 Å. The Fe(6)-F(6) bond length is 2.10 Å. Both Fe(6)-F(3) bond lengths are 2.10 Å. There is one shorter (2.09 Å) and one longer (2.10 Å) Fe(6)-F(5) bond length. In the seventh Fe site, Fe(7) is bonded to one O(5), two equivalent O(7), one F(8), and two equivalent F(6) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(6)F6 octahedra, corners with two equivalent Fe(1)O3F3 octahedra, corners with two equivalent Fe(5)O3F3 octahedra, corners with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(7)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 46-55°. The Fe(7)-O(5) bond length is 2.05 Å. Both Fe(7)-O(7) bond lengths are 1.93 Å. The Fe(7)-F(8) bond length is 2.11 Å. There is one shorter (2.11 Å) and one longer (2.14 Å) Fe(7)-F(6) bond length. In the eighth Fe site, Fe(8) is bonded to one O(8), two equivalent O(6), one F(5), and two equivalent F(7) atoms to form FeO3F3 octahedra that share corners with two equivalent Fe(6)F6 octahedra, corners with two equivalent Fe(1)O3F3 octahedra, corners with two equivalent Fe(5)O3F3 octahedra, corners with two equivalent Fe(2)O6 octahedra, and edges with two equivalent Fe(8)O3F3 octahedra. The corner-sharing octahedral tilt angles range from 45-54°. The Fe(8)-O(8) bond length is 1.96 Å. There is one shorter (1.98 Å) and one longer (2.01 Å) Fe(8)-O(6) bond length. The Fe(8)-F(5) bond length is 2.09 Å. There is one shorter (2.10 Å) and one longer (2.11 Å) Fe(8)-F(7) bond length. There are eight inequivalent O sites. In the first O site, O(1) is bonded in a trigonal planar geometry to one Fe(3) and two equivalent Fe(2) atoms. In the second O site, O(2) is bonded in a trigonal planar geometry to one Fe(4) and two equivalent Fe(1) atoms. In the third O site, O(3) is bonded in a trigonal planar geometry to one Fe(1) and two equivalent Fe(3) atoms. In the fourth O site, O(4) is bonded in a trigonal planar geometry to one Fe(2) and two equivalent Fe(4) atoms. In the fifth O site, O(5) is bonded in a 5-coordinate geometry to two equivalent Li(1), one Fe(7), and two equivalent Fe(5) atoms. In the sixth O site, O(6) is bonded to one Li(1), one Fe(5), and two equivalent Fe(8) atoms to form corner-sharing OLiFe3 trigonal pyramids. In the seventh O site, O(7) is bonded to one Li(1), one Fe(2), and two equivalent Fe(7) atoms to form distorted corner-sharing OLiFe3 trigonal pyramids. In the eighth O site, O(8) is bonded in a 5-coordinate geometry to two equivalent Li(1), one Fe(8), and two equivalent Fe(2) atoms. There are eight inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Fe(5) and two equivalent Fe(3) atoms. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Fe(6) and two equivalent Fe(4) atoms. In the third F site, F(3) is bonded in a distorted trigonal planar geometry to one Fe(3) and two equivalent Fe(6) atoms. In the fourth F site, F(4) is bonded in a distorted trigonal planar geometry to one Fe(4) and two equivalent Fe(5) atoms. In the fifth F site, F(5) is bonded in a distorted trigonal planar geometry to one Fe(8) and two equivalent Fe(6) atoms. In the sixth F site, F(6) is bonded in a distorted T-shaped geometry to one Fe(6) and two equivalent Fe(7) atoms. In the seventh F site, F(7) is bonded in a distorted trigonal planar geometry to one Fe(1) and two equivalent Fe(8) atoms. In the eighth F site, F(8) is bonded in a distorted T-shaped geometry to one Fe(7) and two equivalent Fe(1) atoms.