CsLi3F4 crystallizes in the monoclinic C2/m space group. Cs(1) is bonded in a 2-coordinate geometry to two equivalent F(3) atoms. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(3), two equivalent F(1), and two equivalent F(2) atoms to form a mixture of distorted corner and edge-sharing LiF5 trigonal bipyramids. In the second Li site, Li(2) is bonded to one F(3), two equivalent F(1), and two equivalent F(2) atoms to form a mixture of distorted corner, edge, and face-sharing LiF5 trigonal bipyramids. In the third Li site, Li(3) is bonded to one F(3) and four equivalent F(2) atoms to form a mixture of distorted corner, edge, and face-sharing LiF5 trigonal bipyramids. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Li(2) atoms. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), and two equivalent Li(3) atoms. In the third F site, F(3) is bonded in a 3-coordinate geometry to two equivalent Cs(1), one Li(1), one Li(2), and one Li(3) atom.
CsLi3F4 crystallizes in the monoclinic C2/m space group. Cs(1) is bonded in a 2-coordinate geometry to two equivalent F(3) atoms. Both Cs(1)-F(3) bond lengths are 2.83 Å. There are three inequivalent Li sites. In the first Li site, Li(1) is bonded to one F(3), two equivalent F(1), and two equivalent F(2) atoms to form a mixture of distorted corner and edge-sharing LiF5 trigonal bipyramids. The Li(1)-F(3) bond length is 2.06 Å. Both Li(1)-F(1) bond lengths are 2.08 Å. Both Li(1)-F(2) bond lengths are 2.05 Å. In the second Li site, Li(2) is bonded to one F(3), two equivalent F(1), and two equivalent F(2) atoms to form a mixture of distorted corner, edge, and face-sharing LiF5 trigonal bipyramids. The Li(2)-F(3) bond length is 1.98 Å. Both Li(2)-F(1) bond lengths are 1.99 Å. Both Li(2)-F(2) bond lengths are 2.06 Å. In the third Li site, Li(3) is bonded to one F(3) and four equivalent F(2) atoms to form a mixture of distorted corner, edge, and face-sharing LiF5 trigonal bipyramids. The Li(3)-F(3) bond length is 1.99 Å. There are two shorter (1.94 Å) and two longer (2.19 Å) Li(3)-F(2) bond lengths. There are three inequivalent F sites. In the first F site, F(1) is bonded in a distorted rectangular see-saw-like geometry to two equivalent Li(1) and two equivalent Li(2) atoms. In the second F site, F(2) is bonded in a 4-coordinate geometry to one Li(1), one Li(2), and two equivalent Li(3) atoms. In the third F site, F(3) is bonded in a 3-coordinate geometry to two equivalent Cs(1), one Li(1), one Li(2), and one Li(3) atom.