Ba3Sn4Bi crystallizes in the tetragonal I4/mcm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to eight equivalent Sn(1) and two equivalent Bi(1) atoms. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to eight equivalent Sn(1) and two equivalent Bi(1) atoms. Sn(1) is bonded in a 9-coordinate geometry to two equivalent Ba(1), four equivalent Ba(2), and three equivalent Sn(1) atoms. Bi(1) is bonded to two equivalent Ba(1) and four equivalent Ba(2) atoms to form corner-sharing BiBa6 octahedra. The corner-sharing octahedral tilt angles range from 0-38°.
Ba3Sn4Bi crystallizes in the tetragonal I4/mcm space group. There are two inequivalent Ba sites. In the first Ba site, Ba(1) is bonded in a 10-coordinate geometry to eight equivalent Sn(1) and two equivalent Bi(1) atoms. All Ba(1)-Sn(1) bond lengths are 3.71 Å. Both Ba(1)-Bi(1) bond lengths are 3.36 Å. In the second Ba site, Ba(2) is bonded in a 8-coordinate geometry to eight equivalent Sn(1) and two equivalent Bi(1) atoms. There are a spread of Ba(2)-Sn(1) bond distances ranging from 3.67-4.16 Å. Both Ba(2)-Bi(1) bond lengths are 3.50 Å. Sn(1) is bonded in a 9-coordinate geometry to two equivalent Ba(1), four equivalent Ba(2), and three equivalent Sn(1) atoms. There are two shorter (3.03 Å) and one longer (3.33 Å) Sn(1)-Sn(1) bond length. Bi(1) is bonded to two equivalent Ba(1) and four equivalent Ba(2) atoms to form corner-sharing BiBa6 octahedra. The corner-sharing octahedral tilt angles range from 0-38°.