Pb4Bi crystallizes in the trigonal R-3m space group. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to three equivalent Pb(2) and three equivalent Bi(1) atoms to form distorted PbBi3Pb3 cuboctahedra that share corners with three equivalent Pb(1)Bi3Pb3 cuboctahedra, corners with six equivalent Bi(1)Bi6Pb6 cuboctahedra, corners with nine equivalent Pb(2)Pb12 cuboctahedra, edges with six equivalent Bi(1)Bi6Pb6 cuboctahedra, edges with nine equivalent Pb(1)Bi3Pb3 cuboctahedra, and edges with nine equivalent Pb(2)Pb12 cuboctahedra. In the second Pb site, Pb(2) is bonded to three equivalent Pb(1) and nine equivalent Pb(2) atoms to form PbPb12 cuboctahedra that share corners with three equivalent Bi(1)Bi6Pb6 cuboctahedra, corners with six equivalent Pb(2)Pb12 cuboctahedra, corners with nine equivalent Pb(1)Bi3Pb3 cuboctahedra, edges with three equivalent Bi(1)Bi6Pb6 cuboctahedra, edges with nine equivalent Pb(1)Bi3Pb3 cuboctahedra, edges with twelve equivalent Pb(2)Pb12 cuboctahedra, and faces with twelve equivalent Pb(2)Pb12 cuboctahedra. Bi(1) is bonded to six equivalent Pb(1) and six equivalent Bi(1) atoms to form distorted BiBi6Pb6 cuboctahedra that share corners with six equivalent Pb(2)Pb12 cuboctahedra, corners with six equivalent Bi(1)Bi6Pb6 cuboctahedra, corners with twelve equivalent Pb(1)Bi3Pb3 cuboctahedra, edges with six equivalent Pb(2)Pb12 cuboctahedra, edges with six equivalent Bi(1)Bi6Pb6 cuboctahedra, edges with twelve equivalent Pb(1)Bi3Pb3 cuboctahedra, and faces with six equivalent Bi(1)Bi6Pb6 cuboctahedra.
Pb4Bi crystallizes in the trigonal R-3m space group. There are two inequivalent Pb sites. In the first Pb site, Pb(1) is bonded to three equivalent Pb(2) and three equivalent Bi(1) atoms to form distorted PbBi3Pb3 cuboctahedra that share corners with three equivalent Pb(1)Bi3Pb3 cuboctahedra, corners with six equivalent Bi(1)Bi6Pb6 cuboctahedra, corners with nine equivalent Pb(2)Pb12 cuboctahedra, edges with six equivalent Bi(1)Bi6Pb6 cuboctahedra, edges with nine equivalent Pb(1)Bi3Pb3 cuboctahedra, and edges with nine equivalent Pb(2)Pb12 cuboctahedra. All Pb(1)-Pb(2) bond lengths are 3.55 Å. All Pb(1)-Bi(1) bond lengths are 3.52 Å. In the second Pb site, Pb(2) is bonded to three equivalent Pb(1) and nine equivalent Pb(2) atoms to form PbPb12 cuboctahedra that share corners with three equivalent Bi(1)Bi6Pb6 cuboctahedra, corners with six equivalent Pb(2)Pb12 cuboctahedra, corners with nine equivalent Pb(1)Bi3Pb3 cuboctahedra, edges with three equivalent Bi(1)Bi6Pb6 cuboctahedra, edges with nine equivalent Pb(1)Bi3Pb3 cuboctahedra, edges with twelve equivalent Pb(2)Pb12 cuboctahedra, and faces with twelve equivalent Pb(2)Pb12 cuboctahedra. There are three shorter (3.53 Å) and six longer (3.59 Å) Pb(2)-Pb(2) bond lengths. Bi(1) is bonded to six equivalent Pb(1) and six equivalent Bi(1) atoms to form distorted BiBi6Pb6 cuboctahedra that share corners with six equivalent Pb(2)Pb12 cuboctahedra, corners with six equivalent Bi(1)Bi6Pb6 cuboctahedra, corners with twelve equivalent Pb(1)Bi3Pb3 cuboctahedra, edges with six equivalent Pb(2)Pb12 cuboctahedra, edges with six equivalent Bi(1)Bi6Pb6 cuboctahedra, edges with twelve equivalent Pb(1)Bi3Pb3 cuboctahedra, and faces with six equivalent Bi(1)Bi6Pb6 cuboctahedra. All Bi(1)-Bi(1) bond lengths are 3.59 Å.