K6BiH3(Cl2F)4 crystallizes in the hexagonal P6_3mc space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to one Cl(3), one Cl(4), two equivalent Cl(1), and two equivalent Cl(2) 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 one Cl(3), one Cl(4), two equivalent Cl(1), two equivalent Cl(2), and two equivalent F(2) atoms. Bi(1) is bonded to three equivalent Cl(1) and three equivalent Cl(2) 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 four inequivalent Cl sites. In the first Cl site, Cl(3) is bonded to three equivalent K(1) and three equivalent K(2) atoms to form ClK6 octahedra that share corners with three equivalent Cl(4)K6 octahedra, corners with six equivalent Cl(1)K4Bi square pyramids, edges with three equivalent Cl(1)K4Bi square pyramids, edges with six equivalent Cl(2)K4Bi square pyramids, and  a faceface with one Cl(4)K6 octahedra. The corner-sharing octahedral tilt angles are 3°. In the second Cl site, Cl(4) is bonded to three equivalent K(1) and three equivalent K(2) atoms to form ClK6 octahedra that share corners with three equivalent Cl(3)K6 octahedra, corners with six equivalent Cl(2)K4Bi square pyramids, edges with three equivalent Cl(2)K4Bi square pyramids, edges with six equivalent Cl(1)K4Bi square pyramids, and  a faceface with one Cl(3)K6 octahedra. The corner-sharing octahedral tilt angles are 3°. In the third 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(3)K6 octahedra, corners with two equivalent Cl(1)K4Bi square pyramids, corners with five equivalent Cl(2)K4Bi square pyramids,  an edgeedge with one Cl(3)K6 octahedra, edges with two equivalent Cl(4)K6 octahedra, edges with two equivalent Cl(1)K4Bi square pyramids, and edges with three equivalent Cl(2)K4Bi square pyramids. The corner-sharing octahedral tilt angles are 37°. In the fourth Cl site, Cl(2) is bonded to two equivalent K(1), two equivalent K(2), and one Bi(1) atom to form ClK4Bi square pyramids that share corners with two equivalent Cl(4)K6 octahedra, corners with two equivalent Cl(2)K4Bi square pyramids, corners with five equivalent Cl(1)K4Bi square pyramids,  an edgeedge with one Cl(4)K6 octahedra, edges with two equivalent Cl(3)K6 octahedra, edges with two equivalent Cl(2)K4Bi square pyramids, and edges with three 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_3mc space group. There are two inequivalent K sites. In the first K site, K(1) is bonded to one Cl(3), one Cl(4), two equivalent Cl(1), and two equivalent Cl(2) atoms to form KCl6 octahedra that share edges with two equivalent Bi(1)Cl6 octahedra and edges with four equivalent K(1)Cl6 octahedra. The K(1)-Cl(3) bond length is 3.08 Å. The K(1)-Cl(4) bond length is 3.10 Å. Both K(1)-Cl(1) bond lengths are 3.24 Å. Both K(1)-Cl(2) bond lengths are 3.36 Å. In the second K site, K(2) is bonded in a 8-coordinate geometry to one Cl(3), one Cl(4), two equivalent Cl(1), two equivalent Cl(2), and two equivalent F(2) atoms. The K(2)-Cl(3) bond length is 3.26 Å. The K(2)-Cl(4) bond length is 3.25 Å. Both K(2)-Cl(1) bond lengths are 3.37 Å. Both K(2)-Cl(2) bond lengths are 3.33 Å. Both K(2)-F(2) bond lengths are 2.73 Å. Bi(1) is bonded to three equivalent Cl(1) and three equivalent Cl(2) atoms to form BiCl6 octahedra that share edges with six equivalent K(1)Cl6 octahedra. All Bi(1)-Cl(1) bond lengths are 2.75 Å. All Bi(1)-Cl(2) bond lengths are 2.73 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 1.40 Å. The H(1)-F(2) bond length is 1.01 Å. There are four inequivalent Cl sites. In the first Cl site, Cl(3) is bonded to three equivalent K(1) and three equivalent K(2) atoms to form ClK6 octahedra that share corners with three equivalent Cl(4)K6 octahedra, corners with six equivalent Cl(1)K4Bi square pyramids, edges with three equivalent Cl(1)K4Bi square pyramids, edges with six equivalent Cl(2)K4Bi square pyramids, and  a faceface with one Cl(4)K6 octahedra. The corner-sharing octahedral tilt angles are 3°. In the second Cl site, Cl(4) is bonded to three equivalent K(1) and three equivalent K(2) atoms to form ClK6 octahedra that share corners with three equivalent Cl(3)K6 octahedra, corners with six equivalent Cl(2)K4Bi square pyramids, edges with three equivalent Cl(2)K4Bi square pyramids, edges with six equivalent Cl(1)K4Bi square pyramids, and  a faceface with one Cl(3)K6 octahedra. The corner-sharing octahedral tilt angles are 3°. In the third 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(3)K6 octahedra, corners with two equivalent Cl(1)K4Bi square pyramids, corners with five equivalent Cl(2)K4Bi square pyramids,  an edgeedge with one Cl(3)K6 octahedra, edges with two equivalent Cl(4)K6 octahedra, edges with two equivalent Cl(1)K4Bi square pyramids, and edges with three equivalent Cl(2)K4Bi square pyramids. The corner-sharing octahedral tilt angles are 37°. In the fourth Cl site, Cl(2) is bonded to two equivalent K(1), two equivalent K(2), and one Bi(1) atom to form ClK4Bi square pyramids that share corners with two equivalent Cl(4)K6 octahedra, corners with two equivalent Cl(2)K4Bi square pyramids, corners with five equivalent Cl(1)K4Bi square pyramids,  an edgeedge with one Cl(4)K6 octahedra, edges with two equivalent Cl(3)K6 octahedra, edges with two equivalent Cl(2)K4Bi square pyramids, and edges with three 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.