LiKYF5 crystallizes in the monoclinic P2_1/c space group. K(1) is bonded in a 9-coordinate geometry to one F(2), two equivalent F(1), two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms. Li(1) is bonded to one F(1), one F(2), and two equivalent F(5) atoms to form distorted corner-sharing LiF4 tetrahedra. Y(1) is bonded in a 8-coordinate geometry to one F(1), one F(5), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. There are five inequivalent F sites. In the first F site, F(1) is bonded to two equivalent K(1), one Li(1), and one Y(1) atom to form distorted FK2LiY tetrahedra that share corners with two equivalent F(1)K2LiY tetrahedra, corners with four equivalent F(3)K2Y2 tetrahedra, and  an edgeedge with one F(3)K2Y2 tetrahedra. In the second F site, F(2) is bonded in a 3-coordinate geometry to one K(1), one Li(1), and two equivalent Y(1) atoms. In the third F site, F(3) is bonded to two equivalent K(1) and two equivalent Y(1) atoms to form distorted FK2Y2 tetrahedra that share corners with four equivalent F(1)K2LiY tetrahedra,  an edgeedge with one F(1)K2LiY tetrahedra, and edges with two equivalent F(3)K2Y2 tetrahedra. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to two equivalent K(1) and two equivalent Y(1) atoms. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to two equivalent K(1), two equivalent Li(1), and one Y(1) atom.
LiKYF5 crystallizes in the monoclinic P2_1/c space group. K(1) is bonded in a 9-coordinate geometry to one F(2), two equivalent F(1), two equivalent F(3), two equivalent F(4), and two equivalent F(5) atoms. The K(1)-F(2) bond length is 3.02 Å. Both K(1)-F(1) bond lengths are 2.68 Å. There is one shorter (2.66 Å) and one longer (2.75 Å) K(1)-F(3) bond length. There is one shorter (2.77 Å) and one longer (2.84 Å) K(1)-F(4) bond length. There is one shorter (2.82 Å) and one longer (3.17 Å) K(1)-F(5) bond length. Li(1) is bonded to one F(1), one F(2), and two equivalent F(5) atoms to form distorted corner-sharing LiF4 tetrahedra. The Li(1)-F(1) bond length is 1.89 Å. The Li(1)-F(2) bond length is 1.89 Å. There is one shorter (1.96 Å) and one longer (2.01 Å) Li(1)-F(5) bond length. Y(1) is bonded in a 8-coordinate geometry to one F(1), one F(5), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. The Y(1)-F(1) bond length is 2.23 Å. The Y(1)-F(5) bond length is 2.34 Å. Both Y(1)-F(2) bond lengths are 2.34 Å. There is one shorter (2.24 Å) and one longer (2.36 Å) Y(1)-F(3) bond length. There is one shorter (2.28 Å) and one longer (2.33 Å) Y(1)-F(4) bond length. There are five inequivalent F sites. In the first F site, F(1) is bonded to two equivalent K(1), one Li(1), and one Y(1) atom to form distorted FK2LiY tetrahedra that share corners with two equivalent F(1)K2LiY tetrahedra, corners with four equivalent F(3)K2Y2 tetrahedra, and  an edgeedge with one F(3)K2Y2 tetrahedra. In the second F site, F(2) is bonded in a 3-coordinate geometry to one K(1), one Li(1), and two equivalent Y(1) atoms. In the third F site, F(3) is bonded to two equivalent K(1) and two equivalent Y(1) atoms to form distorted FK2Y2 tetrahedra that share corners with four equivalent F(1)K2LiY tetrahedra,  an edgeedge with one F(1)K2LiY tetrahedra, and edges with two equivalent F(3)K2Y2 tetrahedra. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to two equivalent K(1) and two equivalent Y(1) atoms. In the fifth F site, F(5) is bonded in a 4-coordinate geometry to two equivalent K(1), two equivalent Li(1), and one Y(1) atom.