KBiF4 is alpha bismuth trifluoride-derived structured and crystallizes in the cubic Fd-3m space group. K(1) is bonded in a body-centered cubic geometry to two equivalent F(1) and six equivalent F(2) atoms. Bi(1) is bonded in a distorted body-centered cubic geometry to two equivalent F(3) and six equivalent F(2) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded to four equivalent K(1) atoms to form FK4 tetrahedra that share corners with four equivalent F(1)K4 tetrahedra, corners with twelve equivalent F(2)K2Bi2 tetrahedra, and edges with six equivalent F(2)K2Bi2 tetrahedra. In the second F site, F(2) is bonded to two equivalent K(1) and two equivalent Bi(1) atoms to form FK2Bi2 tetrahedra that share corners with two equivalent F(3)Bi4 tetrahedra, corners with two equivalent F(1)K4 tetrahedra, corners with twelve equivalent F(2)K2Bi2 tetrahedra,  an edgeedge with one F(3)Bi4 tetrahedra,  an edgeedge with one F(1)K4 tetrahedra, and edges with four equivalent F(2)K2Bi2 tetrahedra. In the third F site, F(3) is bonded to four equivalent Bi(1) atoms to form FBi4 tetrahedra that share corners with four equivalent F(3)Bi4 tetrahedra, corners with twelve equivalent F(2)K2Bi2 tetrahedra, and edges with six equivalent F(2)K2Bi2 tetrahedra.
KBiF4 is alpha bismuth trifluoride-derived structured and crystallizes in the cubic Fd-3m space group. K(1) is bonded in a body-centered cubic geometry to two equivalent F(1) and six equivalent F(2) atoms. Both K(1)-F(1) bond lengths are 2.56 Å. All K(1)-F(2) bond lengths are 2.80 Å. Bi(1) is bonded in a distorted body-centered cubic geometry to two equivalent F(3) and six equivalent F(2) atoms. Both Bi(1)-F(3) bond lengths are 2.56 Å. All Bi(1)-F(2) bond lengths are 2.37 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to four equivalent K(1) atoms to form FK4 tetrahedra that share corners with four equivalent F(1)K4 tetrahedra, corners with twelve equivalent F(2)K2Bi2 tetrahedra, and edges with six equivalent F(2)K2Bi2 tetrahedra. In the second F site, F(2) is bonded to two equivalent K(1) and two equivalent Bi(1) atoms to form FK2Bi2 tetrahedra that share corners with two equivalent F(3)Bi4 tetrahedra, corners with two equivalent F(1)K4 tetrahedra, corners with twelve equivalent F(2)K2Bi2 tetrahedra,  an edgeedge with one F(3)Bi4 tetrahedra,  an edgeedge with one F(1)K4 tetrahedra, and edges with four equivalent F(2)K2Bi2 tetrahedra. In the third F site, F(3) is bonded to four equivalent Bi(1) atoms to form FBi4 tetrahedra that share corners with four equivalent F(3)Bi4 tetrahedra, corners with twelve equivalent F(2)K2Bi2 tetrahedra, and edges with six equivalent F(2)K2Bi2 tetrahedra.