K6BiH3(Cl2F)4 crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form KCl6 octahedra that share edges with two equivalent Bi(1)Cl6 octahedra and edges with four equivalent K(1)Cl6 octahedra. In the second K site, K(2) is bonded in a 8-coordinate geometry to two equivalent Cl(2), four equivalent Cl(1), and two equivalent F(2) atoms. Bi(1) is bonded to six equivalent Cl(1) atoms to form BiCl6 octahedra that share edges with six equivalent K(1)Cl6 octahedra. H(1) is bonded in a linear geometry to one F(1) and one F(2) atom. There are two inequivalent Cl sites. In the first Cl site, Cl(2) is bonded to three equivalent K(1) and three equivalent K(2) atoms to form ClK6 octahedra that share corners with three equivalent Cl(2)K6 octahedra, corners with six equivalent Cl(1)K4Bi square pyramids, edges with nine equivalent Cl(1)K4Bi square pyramids, and  a faceface with one Cl(2)K6 octahedra. The corner-sharing octahedra are not tilted. In the second Cl site, Cl(1) is bonded to two equivalent K(1), two equivalent K(2), and one Bi(1) atom to form distorted ClK4Bi square pyramids that share corners with two equivalent Cl(2)K6 octahedra, corners with seven equivalent Cl(1)K4Bi square pyramids, edges with three equivalent Cl(2)K6 octahedra, and edges with five equivalent Cl(1)K4Bi square pyramids. The corner-sharing octahedral tilt angles are 37°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to three equivalent H(1) atoms. In the second F site, F(2) is bonded in a distorted single-bond geometry to two equivalent K(2) and one H(1) atom.
K6BiH3(Cl2F)4 crystallizes in the hexagonal P6_3/mmc space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to two equivalent Cl(2) and four equivalent Cl(1) atoms to form KCl6 octahedra that share edges with two equivalent Bi(1)Cl6 octahedra and edges with four equivalent K(1)Cl6 octahedra. Both K(1)-Cl(2) bond lengths are 3.09 Å. All K(1)-Cl(1) bond lengths are 3.31 Å. In the second K site, K(2) is bonded in a 8-coordinate geometry to two equivalent Cl(2), four equivalent Cl(1), and two equivalent F(2) atoms. Both K(2)-Cl(2) bond lengths are 3.25 Å. All K(2)-Cl(1) bond lengths are 3.35 Å. Both K(2)-F(2) bond lengths are 2.73 Å. Bi(1) is bonded to six equivalent Cl(1) atoms to form BiCl6 octahedra that share edges with six equivalent K(1)Cl6 octahedra. All Bi(1)-Cl(1) bond lengths are 2.74 Å. H(1) is bonded in a linear geometry to one F(1) and one F(2) atom. The H(1)-F(1) bond length is 1.42 Å. The H(1)-F(2) bond length is 1.00 Å. There are two inequivalent Cl sites. In the first Cl site, Cl(2) is bonded to three equivalent K(1) and three equivalent K(2) atoms to form ClK6 octahedra that share corners with three equivalent Cl(2)K6 octahedra, corners with six equivalent Cl(1)K4Bi square pyramids, edges with nine equivalent Cl(1)K4Bi square pyramids, and  a faceface with one Cl(2)K6 octahedra. The corner-sharing octahedra are not tilted. In the second Cl site, Cl(1) is bonded to two equivalent K(1), two equivalent K(2), and one Bi(1) atom to form distorted ClK4Bi square pyramids that share corners with two equivalent Cl(2)K6 octahedra, corners with seven equivalent Cl(1)K4Bi square pyramids, edges with three equivalent Cl(2)K6 octahedra, and edges with five equivalent Cl(1)K4Bi square pyramids. The corner-sharing octahedral tilt angles are 37°. There are two inequivalent F sites. In the first F site, F(1) is bonded in a trigonal planar geometry to three equivalent H(1) atoms. In the second F site, F(2) is bonded in a distorted single-bond geometry to two equivalent K(2) and one H(1) atom.