LiKGdF5 crystallizes in the monoclinic P2_1/c space group. K(1) is bonded in a 9-coordinate geometry to one F(4), two equivalent F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(5) atoms. Li(1) is bonded to one F(2), one F(4), one F(5), and two equivalent F(1) atoms to form distorted corner-sharing LiF5 trigonal pyramids. Gd(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 in a 4-coordinate geometry to two equivalent K(1), two equivalent Li(1), and one Gd(1) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to two equivalent K(1), one Li(1), and two equivalent Gd(1) atoms. In the third F site, F(3) is bonded to two equivalent K(1) and two equivalent Gd(1) atoms to form distorted FK2Gd2 tetrahedra that share corners with four equivalent F(5)K2LiGd tetrahedra,  an edgeedge with one F(5)K2LiGd tetrahedra, and edges with two equivalent F(3)K2Gd2 tetrahedra. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one K(1), one Li(1), and two equivalent Gd(1) atoms. In the fifth F site, F(5) is bonded to two equivalent K(1), one Li(1), and one Gd(1) atom to form distorted FK2LiGd tetrahedra that share corners with two equivalent F(5)K2LiGd tetrahedra, corners with four equivalent F(3)K2Gd2 tetrahedra, and  an edgeedge with one F(3)K2Gd2 tetrahedra.
LiKGdF5 crystallizes in the monoclinic P2_1/c space group. K(1) is bonded in a 9-coordinate geometry to one F(4), two equivalent F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(5) atoms. The K(1)-F(4) bond length is 2.97 Å. There is one shorter (2.76 Å) and one longer (3.16 Å) K(1)-F(1) bond length. There is one shorter (2.72 Å) and one longer (2.85 Å) K(1)-F(2) bond length. There is one shorter (2.61 Å) and one longer (2.70 Å) K(1)-F(3) bond length. There is one shorter (2.63 Å) and one longer (2.65 Å) K(1)-F(5) bond length. Li(1) is bonded to one F(2), one F(4), one F(5), and two equivalent F(1) atoms to form distorted corner-sharing LiF5 trigonal pyramids. The Li(1)-F(2) bond length is 2.53 Å. The Li(1)-F(4) bond length is 1.86 Å. The Li(1)-F(5) bond length is 1.84 Å. There is one shorter (1.93 Å) and one longer (1.96 Å) Li(1)-F(1) bond length. Gd(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 Gd(1)-F(1) bond length is 2.35 Å. The Gd(1)-F(5) bond length is 2.25 Å. There is one shorter (2.29 Å) and one longer (2.33 Å) Gd(1)-F(2) bond length. There is one shorter (2.27 Å) and one longer (2.35 Å) Gd(1)-F(3) bond length. There is one shorter (2.33 Å) and one longer (2.35 Å) Gd(1)-F(4) bond length. There are five inequivalent F sites. In the first F site, F(1) is bonded in a 4-coordinate geometry to two equivalent K(1), two equivalent Li(1), and one Gd(1) atom. In the second F site, F(2) is bonded in a 5-coordinate geometry to two equivalent K(1), one Li(1), and two equivalent Gd(1) atoms. In the third F site, F(3) is bonded to two equivalent K(1) and two equivalent Gd(1) atoms to form distorted FK2Gd2 tetrahedra that share corners with four equivalent F(5)K2LiGd tetrahedra,  an edgeedge with one F(5)K2LiGd tetrahedra, and edges with two equivalent F(3)K2Gd2 tetrahedra. In the fourth F site, F(4) is bonded in a 4-coordinate geometry to one K(1), one Li(1), and two equivalent Gd(1) atoms. In the fifth F site, F(5) is bonded to two equivalent K(1), one Li(1), and one Gd(1) atom to form distorted FK2LiGd tetrahedra that share corners with two equivalent F(5)K2LiGd tetrahedra, corners with four equivalent F(3)K2Gd2 tetrahedra, and  an edgeedge with one F(3)K2Gd2 tetrahedra.