K2GdF5 crystallizes in the orthorhombic Pnma space group. K(1) is bonded in a 8-coordinate geometry to two equivalent F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. Gd(1) is bonded to one F(1), one F(3), one F(4), and four equivalent F(2) atoms to form distorted edge-sharing GdF7 pentagonal bipyramids. There are four inequivalent F sites. In the first F site, F(1) is bonded to four equivalent K(1) and one Gd(1) atom to form distorted FK4Gd trigonal bipyramids that share corners with eight equivalent F(2)K2Gd2 tetrahedra, corners with four equivalent F(4)K4Gd trigonal bipyramids, edges with two equivalent F(2)K2Gd2 tetrahedra,  an edgeedge with one F(4)K4Gd trigonal bipyramid, edges with two equivalent F(1)K4Gd trigonal bipyramids, and  a faceface with one F(4)K4Gd trigonal bipyramid. In the second F site, F(2) is bonded to two equivalent K(1) and two equivalent Gd(1) atoms to form distorted FK2Gd2 tetrahedra that share corners with six equivalent F(2)K2Gd2 tetrahedra, corners with two equivalent F(4)K4Gd trigonal bipyramids, corners with four equivalent F(1)K4Gd trigonal bipyramids,  an edgeedge with one F(2)K2Gd2 tetrahedra,  an edgeedge with one F(1)K4Gd trigonal bipyramid, and edges with two equivalent F(4)K4Gd trigonal bipyramids. In the third F site, F(3) is bonded in a 5-coordinate geometry to four equivalent K(1) and one Gd(1) atom. In the fourth F site, F(4) is bonded to four equivalent K(1) and one Gd(1) atom to form distorted FK4Gd trigonal bipyramids that share corners with four equivalent F(2)K2Gd2 tetrahedra, corners with four equivalent F(1)K4Gd trigonal bipyramids, corners with four equivalent F(4)K4Gd trigonal bipyramids, edges with four equivalent F(2)K2Gd2 tetrahedra,  an edgeedge with one F(1)K4Gd trigonal bipyramid, and  a faceface with one F(1)K4Gd trigonal bipyramid.
K2GdF5 crystallizes in the orthorhombic Pnma space group. K(1) is bonded in a 8-coordinate geometry to two equivalent F(1), two equivalent F(2), two equivalent F(3), and two equivalent F(4) atoms. There is one shorter (2.64 Å) and one longer (2.73 Å) K(1)-F(1) bond length. There is one shorter (2.73 Å) and one longer (2.80 Å) K(1)-F(2) bond length. There is one shorter (2.75 Å) and one longer (2.83 Å) K(1)-F(3) bond length. There is one shorter (2.65 Å) and one longer (2.73 Å) K(1)-F(4) bond length. Gd(1) is bonded to one F(1), one F(3), one F(4), and four equivalent F(2) atoms to form distorted edge-sharing GdF7 pentagonal bipyramids. The Gd(1)-F(1) bond length is 2.23 Å. The Gd(1)-F(3) bond length is 2.23 Å. The Gd(1)-F(4) bond length is 2.25 Å. All Gd(1)-F(2) bond lengths are 2.31 Å. There are four inequivalent F sites. In the first F site, F(1) is bonded to four equivalent K(1) and one Gd(1) atom to form distorted FK4Gd trigonal bipyramids that share corners with eight equivalent F(2)K2Gd2 tetrahedra, corners with four equivalent F(4)K4Gd trigonal bipyramids, edges with two equivalent F(2)K2Gd2 tetrahedra,  an edgeedge with one F(4)K4Gd trigonal bipyramid, edges with two equivalent F(1)K4Gd trigonal bipyramids, and  a faceface with one F(4)K4Gd trigonal bipyramid. In the second F site, F(2) is bonded to two equivalent K(1) and two equivalent Gd(1) atoms to form distorted FK2Gd2 tetrahedra that share corners with six equivalent F(2)K2Gd2 tetrahedra, corners with two equivalent F(4)K4Gd trigonal bipyramids, corners with four equivalent F(1)K4Gd trigonal bipyramids,  an edgeedge with one F(2)K2Gd2 tetrahedra,  an edgeedge with one F(1)K4Gd trigonal bipyramid, and edges with two equivalent F(4)K4Gd trigonal bipyramids. In the third F site, F(3) is bonded in a 5-coordinate geometry to four equivalent K(1) and one Gd(1) atom. In the fourth F site, F(4) is bonded to four equivalent K(1) and one Gd(1) atom to form distorted FK4Gd trigonal bipyramids that share corners with four equivalent F(2)K2Gd2 tetrahedra, corners with four equivalent F(1)K4Gd trigonal bipyramids, corners with four equivalent F(4)K4Gd trigonal bipyramids, edges with four equivalent F(2)K2Gd2 tetrahedra,  an edgeedge with one F(1)K4Gd trigonal bipyramid, and  a faceface with one F(1)K4Gd trigonal bipyramid.