Ba5Bi3 crystallizes in the hexagonal P6_3/mcm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to six equivalent Bi(1) atoms to form a mixture of distorted edge, face, and corner-sharing BaBi6 octahedra. The corner-sharing octahedral tilt angles are 35°. In the second Ba site, Ba(2) is bonded in a 3-coordinate geometry to five equivalent Bi(1) atoms. Bi(1) is bonded in a 9-coordinate geometry to four equivalent Ba(1) and five equivalent Ba(2) atoms.
Ba5Bi3 crystallizes in the hexagonal P6_3/mcm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to six equivalent Bi(1) atoms to form a mixture of distorted edge, face, and corner-sharing BaBi6 octahedra. The corner-sharing octahedral tilt angles are 35°. All Ba(1)-Bi(1) bond lengths are 3.75 Å. In the second Ba site, Ba(2) is bonded in a 3-coordinate geometry to five equivalent Bi(1) atoms. There are a spread of Ba(2)-Bi(1) bond distances ranging from 3.54-4.24 Å. Bi(1) is bonded in a 9-coordinate geometry to four equivalent Ba(1) and five equivalent Ba(2) atoms.