KLiHoF5 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(4), one F(5), and two equivalent F(1) atoms to form distorted corner-sharing LiF4 tetrahedra. Ho(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 Ho(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to two equivalent K(1) and two equivalent Ho(1) atoms. In the third F site, F(3) is bonded to two equivalent K(1) and two equivalent Ho(1) atoms to form distorted FK2Ho2 tetrahedra that share corners with four equivalent F(5)K2LiHo tetrahedra,  an edgeedge with one F(5)K2LiHo tetrahedra, and edges with two equivalent F(3)K2Ho2 tetrahedra. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one K(1), one Li(1), and two equivalent Ho(1) atoms. In the fifth F site, F(5) is bonded to two equivalent K(1), one Li(1), and one Ho(1) atom to form distorted FK2LiHo tetrahedra that share corners with two equivalent F(5)K2LiHo tetrahedra, corners with four equivalent F(3)K2Ho2 tetrahedra, and  an edgeedge with one F(3)K2Ho2 tetrahedra.
KLiHoF5 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 3.00 Å. There is one shorter (2.82 Å) and one longer (3.16 Å) K(1)-F(1) bond length. There is one shorter (2.76 Å) and one longer (2.82 Å) K(1)-F(2) bond length. There is one shorter (2.64 Å) and one longer (2.74 Å) K(1)-F(3) bond length. Both K(1)-F(5) bond lengths are 2.68 Å. Li(1) is bonded to one F(4), one F(5), and two equivalent F(1) atoms to form distorted corner-sharing LiF4 tetrahedra. The Li(1)-F(4) bond length is 1.89 Å. The Li(1)-F(5) bond length is 1.88 Å. There is one shorter (1.96 Å) and one longer (2.00 Å) Li(1)-F(1) bond length. Ho(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 Ho(1)-F(1) bond length is 2.32 Å. The Ho(1)-F(5) bond length is 2.22 Å. There is one shorter (2.26 Å) and one longer (2.32 Å) Ho(1)-F(2) bond length. There is one shorter (2.23 Å) and one longer (2.34 Å) Ho(1)-F(3) bond length. Both Ho(1)-F(4) bond lengths are 2.32 Å. 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 Ho(1) atom. In the second F site, F(2) is bonded in a 4-coordinate geometry to two equivalent K(1) and two equivalent Ho(1) atoms. In the third F site, F(3) is bonded to two equivalent K(1) and two equivalent Ho(1) atoms to form distorted FK2Ho2 tetrahedra that share corners with four equivalent F(5)K2LiHo tetrahedra,  an edgeedge with one F(5)K2LiHo tetrahedra, and edges with two equivalent F(3)K2Ho2 tetrahedra. In the fourth F site, F(4) is bonded in a 3-coordinate geometry to one K(1), one Li(1), and two equivalent Ho(1) atoms. In the fifth F site, F(5) is bonded to two equivalent K(1), one Li(1), and one Ho(1) atom to form distorted FK2LiHo tetrahedra that share corners with two equivalent F(5)K2LiHo tetrahedra, corners with four equivalent F(3)K2Ho2 tetrahedra, and  an edgeedge with one F(3)K2Ho2 tetrahedra.