Ba4(Sn3Bi)3 crystallizes in the hexagonal P6_3/mmc space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to three equivalent Sn(2), six equivalent Sn(1), and three equivalent Bi(1) atoms to form distorted BaSn9Bi3 cuboctahedra that share corners with nine equivalent Ba(1)Sn9Bi3 cuboctahedra,  a faceface with one Ba(1)Sn9Bi3 cuboctahedra, faces with three equivalent Ba(3)Sn12 cuboctahedra, and faces with three equivalent Ba(2)Sn6Bi6 cuboctahedra. In the second Ba site, Ba(2) is bonded to six equivalent Sn(1) and six equivalent Bi(1) atoms to form BaSn6Bi6 cuboctahedra that share corners with six equivalent Ba(2)Sn6Bi6 cuboctahedra, faces with two equivalent Ba(3)Sn12 cuboctahedra, and faces with six equivalent Ba(1)Sn9Bi3 cuboctahedra. In the third Ba site, Ba(3) is bonded to six equivalent Sn(1) and six equivalent Sn(2) atoms to form distorted BaSn12 cuboctahedra that share corners with six equivalent Ba(3)Sn12 cuboctahedra, faces with two equivalent Ba(2)Sn6Bi6 cuboctahedra, and faces with six equivalent Ba(1)Sn9Bi3 cuboctahedra. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 10-coordinate geometry to one Ba(2), one Ba(3), two equivalent Ba(1), two equivalent Sn(1), two equivalent Sn(2), and two equivalent Bi(1) atoms. In the second Sn site, Sn(2) is bonded in a 10-coordinate geometry to two equivalent Ba(1), two equivalent Ba(3), two equivalent Sn(2), and four equivalent Sn(1) atoms. Bi(1) is bonded in a 8-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), and four equivalent Sn(1) atoms.
Ba4(Sn3Bi)3 crystallizes in the hexagonal P6_3/mmc space group. There are three inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to three equivalent Sn(2), six equivalent Sn(1), and three equivalent Bi(1) atoms to form distorted BaSn9Bi3 cuboctahedra that share corners with nine equivalent Ba(1)Sn9Bi3 cuboctahedra,  a faceface with one Ba(1)Sn9Bi3 cuboctahedra, faces with three equivalent Ba(3)Sn12 cuboctahedra, and faces with three equivalent Ba(2)Sn6Bi6 cuboctahedra. All Ba(1)-Sn(2) bond lengths are 3.60 Å. All Ba(1)-Sn(1) bond lengths are 3.74 Å. All Ba(1)-Bi(1) bond lengths are 3.71 Å. In the second Ba site, Ba(2) is bonded to six equivalent Sn(1) and six equivalent Bi(1) atoms to form BaSn6Bi6 cuboctahedra that share corners with six equivalent Ba(2)Sn6Bi6 cuboctahedra, faces with two equivalent Ba(3)Sn12 cuboctahedra, and faces with six equivalent Ba(1)Sn9Bi3 cuboctahedra. All Ba(2)-Sn(1) bond lengths are 3.76 Å. All Ba(2)-Bi(1) bond lengths are 3.71 Å. In the third Ba site, Ba(3) is bonded to six equivalent Sn(1) and six equivalent Sn(2) atoms to form distorted BaSn12 cuboctahedra that share corners with six equivalent Ba(3)Sn12 cuboctahedra, faces with two equivalent Ba(2)Sn6Bi6 cuboctahedra, and faces with six equivalent Ba(1)Sn9Bi3 cuboctahedra. All Ba(3)-Sn(1) bond lengths are 3.77 Å. All Ba(3)-Sn(2) bond lengths are 3.74 Å. There are two inequivalent Sn sites. In the first Sn site, Sn(1) is bonded in a 10-coordinate geometry to one Ba(2), one Ba(3), two equivalent Ba(1), two equivalent Sn(1), two equivalent Sn(2), and two equivalent Bi(1) atoms. Both Sn(1)-Sn(1) bond lengths are 3.03 Å. Both Sn(1)-Sn(2) bond lengths are 3.29 Å. Both Sn(1)-Bi(1) bond lengths are 3.41 Å. In the second Sn site, Sn(2) is bonded in a 10-coordinate geometry to two equivalent Ba(1), two equivalent Ba(3), two equivalent Sn(2), and four equivalent Sn(1) atoms. Both Sn(2)-Sn(2) bond lengths are 3.01 Å. Bi(1) is bonded in a 8-coordinate geometry to two equivalent Ba(1), two equivalent Ba(2), and four equivalent Sn(1) atoms.