LiMn2O2F3 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. Mn(1) is bonded to three equivalent O(1), one F(1), and two equivalent F(2) atoms to form a mixture of distorted corner and edge-sharing MnO3F3 octahedra. The corner-sharing octahedral tilt angles range from 21-49°. O(1) is bonded to one Li(1) and three equivalent Mn(1) atoms to form distorted OLiMn3 trigonal pyramids that share  a cornercorner with one F(1)Li2Mn2 trigonal pyramid, corners with three equivalent O(1)LiMn3 trigonal pyramids, edges with two equivalent O(1)LiMn3 trigonal pyramids, and edges with two equivalent F(1)Li2Mn2 trigonal pyramids. There are two inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1) and two equivalent Mn(1) atoms to form distorted FLi2Mn2 trigonal pyramids that share corners with two equivalent O(1)LiMn3 trigonal pyramids, corners with two equivalent F(1)Li2Mn2 trigonal pyramids, and edges with four equivalent O(1)LiMn3 trigonal pyramids. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent Mn(1) atoms.
LiMn2O2F3 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 2.46 Å. Both Li(1)-F(1) bond lengths are 2.06 Å. Both Li(1)-F(2) bond lengths are 1.95 Å. Mn(1) is bonded to three equivalent O(1), one F(1), and two equivalent F(2) atoms to form a mixture of distorted corner and edge-sharing MnO3F3 octahedra. The corner-sharing octahedral tilt angles range from 21-49°. All Mn(1)-O(1) bond lengths are 1.93 Å. The Mn(1)-F(1) bond length is 2.23 Å. There is one shorter (1.93 Å) and one longer (2.27 Å) Mn(1)-F(2) bond length. O(1) is bonded to one Li(1) and three equivalent Mn(1) atoms to form distorted OLiMn3 trigonal pyramids that share  a cornercorner with one F(1)Li2Mn2 trigonal pyramid, corners with three equivalent O(1)LiMn3 trigonal pyramids, edges with two equivalent O(1)LiMn3 trigonal pyramids, and edges with two equivalent F(1)Li2Mn2 trigonal pyramids. There are two inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Li(1) and two equivalent Mn(1) atoms to form distorted FLi2Mn2 trigonal pyramids that share corners with two equivalent O(1)LiMn3 trigonal pyramids, corners with two equivalent F(1)Li2Mn2 trigonal pyramids, and edges with four equivalent O(1)LiMn3 trigonal pyramids. In the second F site, F(2) is bonded in a distorted T-shaped geometry to one Li(1) and two equivalent Mn(1) atoms.