Li5MnO3F is pyrite-derived structured and crystallizes in the orthorhombic Pnma space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal planar geometry to one O(2) and two equivalent O(1) atoms. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(2), two equivalent O(1), and one F(1) atom. In the third Li site, Li(3) is bonded to one O(2), two equivalent O(1), and one F(1) atom to form LiO3F tetrahedra that share corners with four equivalent Mn(1)O3F tetrahedra. Mn(1) is bonded to one O(2), two equivalent O(1), and one F(1) atom to form MnO3F tetrahedra that share corners with four equivalent Li(3)O3F tetrahedra. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Mn(1) atom to form OLi5Mn octahedra that share corners with two equivalent O(1)Li5Mn octahedra, corners with four equivalent F(1)Li3Mn tetrahedra, and edges with two equivalent O(1)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 55-61°. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Mn(1) atom. F(1) is bonded to one Li(3), two equivalent Li(2), and one Mn(1) atom to form distorted FLi3Mn tetrahedra that share corners with eight equivalent O(1)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 57-75°.
Li5MnO3F is pyrite-derived structured and crystallizes in the orthorhombic Pnma space group. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded in a distorted trigonal planar geometry to one O(2) and two equivalent O(1) atoms. The Li(1)-O(2) bond length is 1.91 Å. There is one shorter (1.98 Å) and one longer (1.99 Å) Li(1)-O(1) bond length. In the second Li site, Li(2) is bonded in a 4-coordinate geometry to one O(2), two equivalent O(1), and one F(1) atom. The Li(2)-O(2) bond length is 2.27 Å. There is one shorter (1.99 Å) and one longer (2.06 Å) Li(2)-O(1) bond length. The Li(2)-F(1) bond length is 1.95 Å. In the third Li site, Li(3) is bonded to one O(2), two equivalent O(1), and one F(1) atom to form LiO3F tetrahedra that share corners with four equivalent Mn(1)O3F tetrahedra. The Li(3)-O(2) bond length is 1.93 Å. Both Li(3)-O(1) bond lengths are 2.00 Å. The Li(3)-F(1) bond length is 2.03 Å. Mn(1) is bonded to one O(2), two equivalent O(1), and one F(1) atom to form MnO3F tetrahedra that share corners with four equivalent Li(3)O3F tetrahedra. The Mn(1)-O(2) bond length is 2.00 Å. Both Mn(1)-O(1) bond lengths are 2.02 Å. The Mn(1)-F(1) bond length is 2.18 Å. There are two inequivalent O sites. In the first O site, O(1) is bonded to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Mn(1) atom to form OLi5Mn octahedra that share corners with two equivalent O(1)Li5Mn octahedra, corners with four equivalent F(1)Li3Mn tetrahedra, and edges with two equivalent O(1)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 55-61°. In the second O site, O(2) is bonded in a 6-coordinate geometry to one Li(3), two equivalent Li(1), two equivalent Li(2), and one Mn(1) atom. F(1) is bonded to one Li(3), two equivalent Li(2), and one Mn(1) atom to form distorted FLi3Mn tetrahedra that share corners with eight equivalent O(1)Li5Mn octahedra. The corner-sharing octahedral tilt angles range from 57-75°.