(Pb2BiF6)2F2 is Fluorite-derived structured and crystallizes in the tetragonal I4/mmm space group. The structure consists of two hydrofluoric acid atoms inside a Pb2BiF6 framework. In the Pb2BiF6 framework, Pb(1) is bonded in a body-centered cubic geometry to four equivalent F(1) and four equivalent F(2) atoms. Bi(1) is bonded in a body-centered cubic geometry to eight equivalent F(2) atoms. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Pb(1) atoms to form FPb4 tetrahedra that share corners with four equivalent F(1)Pb4 tetrahedra, corners with twelve equivalent F(2)Bi2Pb2 tetrahedra, edges with two equivalent F(2)Bi2Pb2 tetrahedra, and edges with four equivalent F(1)Pb4 tetrahedra. In the second F site, F(2) is bonded to two equivalent Pb(1) and two equivalent Bi(1) atoms to form FBi2Pb2 tetrahedra that share corners with six equivalent F(1)Pb4 tetrahedra, corners with ten equivalent F(2)Bi2Pb2 tetrahedra,  an edgeedge with one F(1)Pb4 tetrahedra, and edges with five equivalent F(2)Bi2Pb2 tetrahedra.
(Pb2BiF6)2F2 is Fluorite-derived structured and crystallizes in the tetragonal I4/mmm space group. The structure consists of two hydrofluoric acid atoms inside a Pb2BiF6 framework. In the Pb2BiF6 framework, Pb(1) is bonded in a body-centered cubic geometry to four equivalent F(1) and four equivalent F(2) atoms. All Pb(1)-F(1) bond lengths are 2.56 Å. All Pb(1)-F(2) bond lengths are 2.53 Å. Bi(1) is bonded in a body-centered cubic geometry to eight equivalent F(2) atoms. All Bi(1)-F(2) bond lengths are 2.56 Å. There are two inequivalent F sites. In the first F site, F(1) is bonded to four equivalent Pb(1) atoms to form FPb4 tetrahedra that share corners with four equivalent F(1)Pb4 tetrahedra, corners with twelve equivalent F(2)Bi2Pb2 tetrahedra, edges with two equivalent F(2)Bi2Pb2 tetrahedra, and edges with four equivalent F(1)Pb4 tetrahedra. In the second F site, F(2) is bonded to two equivalent Pb(1) and two equivalent Bi(1) atoms to form FBi2Pb2 tetrahedra that share corners with six equivalent F(1)Pb4 tetrahedra, corners with ten equivalent F(2)Bi2Pb2 tetrahedra,  an edgeedge with one F(1)Pb4 tetrahedra, and edges with five equivalent F(2)Bi2Pb2 tetrahedra.