LiFe2O2F3 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms. Fe(1) is bonded to three equivalent O(1), one F(2), and two equivalent F(1) atoms to form a mixture of corner and edge-sharing FeO3F3 octahedra. The corner-sharing octahedral tilt angles range from 21-45°. O(1) is bonded to one Li(1) and three equivalent Fe(1) atoms to form distorted OLiFe3 trigonal pyramids that share  a cornercorner with one F(2)Li2Fe2 trigonal pyramid, corners with three equivalent O(1)LiFe3 trigonal pyramids, edges with two equivalent O(1)LiFe3 trigonal pyramids, and edges with two equivalent F(2)Li2Fe2 trigonal pyramids. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent Fe(1) atoms. In the second F site, F(2) is bonded to two equivalent Li(1) and two equivalent Fe(1) atoms to form distorted FLi2Fe2 trigonal pyramids that share corners with two equivalent O(1)LiFe3 trigonal pyramids, corners with two equivalent F(2)Li2Fe2 trigonal pyramids, and edges with four equivalent O(1)LiFe3 trigonal pyramids.
LiFe2O2F3 is beta indium sulfide-derived structured and crystallizes in the orthorhombic Cmcm space group. Li(1) is bonded in a 6-coordinate geometry to two equivalent O(1), two equivalent F(1), and two equivalent F(2) atoms. Both Li(1)-O(1) bond lengths are 2.29 Å. Both Li(1)-F(1) bond lengths are 1.99 Å. Both Li(1)-F(2) bond lengths are 2.07 Å. Fe(1) is bonded to three equivalent O(1), one F(2), and two equivalent F(1) atoms to form a mixture of corner and edge-sharing FeO3F3 octahedra. The corner-sharing octahedral tilt angles range from 21-45°. There are two shorter (1.95 Å) and one longer (2.02 Å) Fe(1)-O(1) bond length. The Fe(1)-F(2) bond length is 2.14 Å. There is one shorter (2.01 Å) and one longer (2.09 Å) Fe(1)-F(1) bond length. O(1) is bonded to one Li(1) and three equivalent Fe(1) atoms to form distorted OLiFe3 trigonal pyramids that share  a cornercorner with one F(2)Li2Fe2 trigonal pyramid, corners with three equivalent O(1)LiFe3 trigonal pyramids, edges with two equivalent O(1)LiFe3 trigonal pyramids, and edges with two equivalent F(2)Li2Fe2 trigonal pyramids. There are two inequivalent F sites. In the first F site, F(1) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent Fe(1) atoms. In the second F site, F(2) is bonded to two equivalent Li(1) and two equivalent Fe(1) atoms to form distorted FLi2Fe2 trigonal pyramids that share corners with two equivalent O(1)LiFe3 trigonal pyramids, corners with two equivalent F(2)Li2Fe2 trigonal pyramids, and edges with four equivalent O(1)LiFe3 trigonal pyramids.