PbBi2F8 crystallizes in the tetragonal I4/mmm space group. Pb(1) is bonded in a body-centered cubic geometry to eight equivalent F(1) atoms. Bi(1) is bonded in a distorted q6 geometry to one F(3), four equivalent F(1), and four equivalent F(2) atoms. There are three inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Pb(1) and two equivalent Bi(1) atoms to form FBi2Pb2 tetrahedra that share corners with six equivalent F(2)Bi4 tetrahedra, corners with ten equivalent F(1)Bi2Pb2 tetrahedra,  an edgeedge with one F(2)Bi4 tetrahedra, and edges with five equivalent F(1)Bi2Pb2 tetrahedra. In the second F site, F(2) is bonded to four equivalent Bi(1) atoms to form FBi4 tetrahedra that share corners with four equivalent F(2)Bi4 tetrahedra, corners with twelve equivalent F(1)Bi2Pb2 tetrahedra, edges with two equivalent F(1)Bi2Pb2 tetrahedra, and edges with four equivalent F(2)Bi4 tetrahedra. In the third F site, F(3) is bonded in a single-bond geometry to one Bi(1) atom.
PbBi2F8 crystallizes in the tetragonal I4/mmm space group. Pb(1) is bonded in a body-centered cubic geometry to eight equivalent F(1) atoms. All Pb(1)-F(1) bond lengths are 2.60 Å. Bi(1) is bonded in a distorted q6 geometry to one F(3), four equivalent F(1), and four equivalent F(2) atoms. The Bi(1)-F(3) bond length is 2.26 Å. All Bi(1)-F(1) bond lengths are 2.62 Å. All Bi(1)-F(2) bond lengths are 2.47 Å. There are three inequivalent F sites. In the first F site, F(1) is bonded to two equivalent Pb(1) and two equivalent Bi(1) atoms to form FBi2Pb2 tetrahedra that share corners with six equivalent F(2)Bi4 tetrahedra, corners with ten equivalent F(1)Bi2Pb2 tetrahedra,  an edgeedge with one F(2)Bi4 tetrahedra, and edges with five equivalent F(1)Bi2Pb2 tetrahedra. In the second F site, F(2) is bonded to four equivalent Bi(1) atoms to form FBi4 tetrahedra that share corners with four equivalent F(2)Bi4 tetrahedra, corners with twelve equivalent F(1)Bi2Pb2 tetrahedra, edges with two equivalent F(1)Bi2Pb2 tetrahedra, and edges with four equivalent F(2)Bi4 tetrahedra. In the third F site, F(3) is bonded in a single-bond geometry to one Bi(1) atom.