Li6MnO3F2 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form a mixture of distorted edge and corner-sharing LiO2F2 trigonal pyramids. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent F(1) atoms to form a mixture of distorted edge and corner-sharing LiO2F2 tetrahedra. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one O(2), two equivalent O(1), and one F(1) atom. Mn(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(1), and two equivalent F(1) atoms. There are two inequivalent O sites. In the first O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(3), and one Mn(1) atom to form a mixture of distorted edge and corner-sharing OLi4Mn trigonal bipyramids. In the second O site, O(1) is bonded to one Li(1), two equivalent Li(2), two equivalent Li(3), and one Mn(1) atom to form distorted OLi5Mn pentagonal pyramids that share  a cornercorner with one O(1)Li5Mn pentagonal pyramid, corners with two equivalent O(2)Li4Mn trigonal bipyramids, edges with two equivalent O(1)Li5Mn pentagonal pyramids, and  an edgeedge with one O(2)Li4Mn trigonal bipyramid. F(1) is bonded in a 6-coordinate geometry to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Mn(1) atom.
Li6MnO3F2 crystallizes in the monoclinic C2/c space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one O(1), one O(2), and two equivalent F(1) atoms to form a mixture of distorted edge and corner-sharing LiO2F2 trigonal pyramids. The Li(1)-O(1) bond length is 2.02 Å. The Li(1)-O(2) bond length is 1.95 Å. There is one shorter (1.94 Å) and one longer (2.08 Å) Li(1)-F(1) bond length. In the second Li site, Li(2) is bonded to two equivalent O(1) and two equivalent F(1) atoms to form a mixture of distorted edge and corner-sharing LiO2F2 tetrahedra. There is one shorter (1.95 Å) and one longer (1.96 Å) Li(2)-O(1) bond length. There is one shorter (1.95 Å) and one longer (2.06 Å) Li(2)-F(1) bond length. In the third Li site, Li(3) is bonded in a 3-coordinate geometry to one O(2), two equivalent O(1), and one F(1) atom. The Li(3)-O(2) bond length is 1.87 Å. There is one shorter (1.92 Å) and one longer (2.12 Å) Li(3)-O(1) bond length. The Li(3)-F(1) bond length is 2.56 Å. Mn(1) is bonded in a 5-coordinate geometry to one O(2), two equivalent O(1), and two equivalent F(1) atoms. The Mn(1)-O(2) bond length is 1.99 Å. Both Mn(1)-O(1) bond lengths are 2.10 Å. Both Mn(1)-F(1) bond lengths are 2.46 Å. There are two inequivalent O sites. In the first O site, O(2) is bonded to two equivalent Li(1), two equivalent Li(3), and one Mn(1) atom to form a mixture of distorted edge and corner-sharing OLi4Mn trigonal bipyramids. In the second O site, O(1) is bonded to one Li(1), two equivalent Li(2), two equivalent Li(3), and one Mn(1) atom to form distorted OLi5Mn pentagonal pyramids that share  a cornercorner with one O(1)Li5Mn pentagonal pyramid, corners with two equivalent O(2)Li4Mn trigonal bipyramids, edges with two equivalent O(1)Li5Mn pentagonal pyramids, and  an edgeedge with one O(2)Li4Mn trigonal bipyramid. F(1) is bonded in a 6-coordinate geometry to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Mn(1) atom.