Li4MnOF4 crystallizes in the tetragonal I4/m space group. Li(1) is bonded to one O(1) and four equivalent F(1) atoms to form LiOF4 trigonal bipyramids that share corners with two equivalent Mn(1)O2F4 octahedra, corners with five equivalent Li(1)OF4 trigonal bipyramids, edges with two equivalent Mn(1)O2F4 octahedra, and edges with five equivalent Li(1)OF4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 28-64°. Mn(1) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form MnO2F4 octahedra that share corners with two equivalent Mn(1)O2F4 octahedra, corners with eight equivalent Li(1)OF4 trigonal bipyramids, and edges with eight equivalent Li(1)OF4 trigonal bipyramids. The corner-sharing octahedra are not tilted. O(1) is bonded to four equivalent Li(1) and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with eight equivalent F(1)Li4Mn trigonal bipyramids, and edges with eight equivalent F(1)Li4Mn trigonal bipyramids. The corner-sharing octahedra are not tilted. F(1) is bonded to four equivalent Li(1) and one Mn(1) atom to form FLi4Mn trigonal bipyramids that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with five equivalent F(1)Li4Mn trigonal bipyramids, edges with two equivalent O(1)Li4Mn2 octahedra, and edges with five equivalent F(1)Li4Mn trigonal bipyramids. The corner-sharing octahedral tilt angles range from 28-60°.
Li4MnOF4 crystallizes in the tetragonal I4/m space group. Li(1) is bonded to one O(1) and four equivalent F(1) atoms to form LiOF4 trigonal bipyramids that share corners with two equivalent Mn(1)O2F4 octahedra, corners with five equivalent Li(1)OF4 trigonal bipyramids, edges with two equivalent Mn(1)O2F4 octahedra, and edges with five equivalent Li(1)OF4 trigonal bipyramids. The corner-sharing octahedral tilt angles range from 28-64°. The Li(1)-O(1) bond length is 2.12 Å. There are a spread of Li(1)-F(1) bond distances ranging from 1.94-2.08 Å. Mn(1) is bonded to two equivalent O(1) and four equivalent F(1) atoms to form MnO2F4 octahedra that share corners with two equivalent Mn(1)O2F4 octahedra, corners with eight equivalent Li(1)OF4 trigonal bipyramids, and edges with eight equivalent Li(1)OF4 trigonal bipyramids. The corner-sharing octahedra are not tilted. Both Mn(1)-O(1) bond lengths are 2.06 Å. All Mn(1)-F(1) bond lengths are 2.21 Å. O(1) is bonded to four equivalent Li(1) and two equivalent Mn(1) atoms to form OLi4Mn2 octahedra that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with eight equivalent F(1)Li4Mn trigonal bipyramids, and edges with eight equivalent F(1)Li4Mn trigonal bipyramids. The corner-sharing octahedra are not tilted. F(1) is bonded to four equivalent Li(1) and one Mn(1) atom to form FLi4Mn trigonal bipyramids that share corners with two equivalent O(1)Li4Mn2 octahedra, corners with five equivalent F(1)Li4Mn trigonal bipyramids, edges with two equivalent O(1)Li4Mn2 octahedra, and edges with five equivalent F(1)Li4Mn trigonal bipyramids. The corner-sharing octahedral tilt angles range from 28-60°.