Ag3Bi crystallizes in the hexagonal P-6m2 space group. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to six equivalent Ag(1) and six equivalent Ag(2) atoms to form AgAg12 cuboctahedra that share corners with six equivalent Ag(1)Ag12 cuboctahedra, corners with twelve equivalent Bi(1)Ag6Bi6 cuboctahedra, edges with six equivalent Ag(1)Ag12 cuboctahedra, edges with twelve equivalent Ag(2)Ag9Bi3 cuboctahedra, faces with two equivalent Bi(1)Ag6Bi6 cuboctahedra, faces with six equivalent Ag(1)Ag12 cuboctahedra, and faces with twelve equivalent Ag(2)Ag9Bi3 cuboctahedra. In the second Ag site, Ag(2) is bonded to three equivalent Ag(1), six equivalent Ag(2), and three equivalent Bi(1) atoms to form AgAg9Bi3 cuboctahedra that share corners with eighteen equivalent Ag(2)Ag9Bi3 cuboctahedra, edges with six equivalent Ag(1)Ag12 cuboctahedra, edges with six equivalent Ag(2)Ag9Bi3 cuboctahedra, edges with six equivalent Bi(1)Ag6Bi6 cuboctahedra, faces with six equivalent Ag(1)Ag12 cuboctahedra, faces with six equivalent Bi(1)Ag6Bi6 cuboctahedra, and faces with eight equivalent Ag(2)Ag9Bi3 cuboctahedra. Bi(1) is bonded to six equivalent Ag(2) and six equivalent Bi(1) atoms to form BiAg6Bi6 cuboctahedra that share corners with six equivalent Bi(1)Ag6Bi6 cuboctahedra, corners with twelve equivalent Ag(1)Ag12 cuboctahedra, edges with six equivalent Bi(1)Ag6Bi6 cuboctahedra, edges with twelve equivalent Ag(2)Ag9Bi3 cuboctahedra, faces with two equivalent Ag(1)Ag12 cuboctahedra, faces with six equivalent Bi(1)Ag6Bi6 cuboctahedra, and faces with twelve equivalent Ag(2)Ag9Bi3 cuboctahedra.
Ag3Bi crystallizes in the hexagonal P-6m2 space group. There are two inequivalent Ag sites. In the first Ag site, Ag(1) is bonded to six equivalent Ag(1) and six equivalent Ag(2) atoms to form AgAg12 cuboctahedra that share corners with six equivalent Ag(1)Ag12 cuboctahedra, corners with twelve equivalent Bi(1)Ag6Bi6 cuboctahedra, edges with six equivalent Ag(1)Ag12 cuboctahedra, edges with twelve equivalent Ag(2)Ag9Bi3 cuboctahedra, faces with two equivalent Bi(1)Ag6Bi6 cuboctahedra, faces with six equivalent Ag(1)Ag12 cuboctahedra, and faces with twelve equivalent Ag(2)Ag9Bi3 cuboctahedra. All Ag(1)-Ag(1) bond lengths are 3.26 Å. All Ag(1)-Ag(2) bond lengths are 2.89 Å. In the second Ag site, Ag(2) is bonded to three equivalent Ag(1), six equivalent Ag(2), and three equivalent Bi(1) atoms to form AgAg9Bi3 cuboctahedra that share corners with eighteen equivalent Ag(2)Ag9Bi3 cuboctahedra, edges with six equivalent Ag(1)Ag12 cuboctahedra, edges with six equivalent Ag(2)Ag9Bi3 cuboctahedra, edges with six equivalent Bi(1)Ag6Bi6 cuboctahedra, faces with six equivalent Ag(1)Ag12 cuboctahedra, faces with six equivalent Bi(1)Ag6Bi6 cuboctahedra, and faces with eight equivalent Ag(2)Ag9Bi3 cuboctahedra. All Ag(2)-Ag(2) bond lengths are 3.26 Å. All Ag(2)-Bi(1) bond lengths are 3.23 Å. Bi(1) is bonded to six equivalent Ag(2) and six equivalent Bi(1) atoms to form BiAg6Bi6 cuboctahedra that share corners with six equivalent Bi(1)Ag6Bi6 cuboctahedra, corners with twelve equivalent Ag(1)Ag12 cuboctahedra, edges with six equivalent Bi(1)Ag6Bi6 cuboctahedra, edges with twelve equivalent Ag(2)Ag9Bi3 cuboctahedra, faces with two equivalent Ag(1)Ag12 cuboctahedra, faces with six equivalent Bi(1)Ag6Bi6 cuboctahedra, and faces with twelve equivalent Ag(2)Ag9Bi3 cuboctahedra. All Bi(1)-Bi(1) bond lengths are 3.26 Å.