BaSn2Bi crystallizes in the monoclinic Cm space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to one Sn(3), two equivalent Sn(4), four equivalent Sn(5), one Bi(3), two equivalent Bi(1), and two equivalent Bi(2) atoms to form BaSn7Bi5 cuboctahedra that share corners with three equivalent Ba(4)Sn9Bi3 cuboctahedra, corners with six equivalent Ba(1)Sn7Bi5 cuboctahedra,  a faceface with one Ba(4)Sn9Bi3 cuboctahedra, faces with three equivalent Ba(3)Sn11Bi cuboctahedra, and faces with three equivalent Ba(2)Sn5Bi7 cuboctahedra. In the second Ba site, Ba(2) is bonded to one Sn(1), two equivalent Sn(2), two equivalent Sn(5), one Bi(1), two equivalent Bi(3), and four equivalent Bi(2) atoms to form BaSn5Bi7 cuboctahedra that share corners with three equivalent Ba(3)Sn11Bi cuboctahedra, corners with six equivalent Ba(2)Sn5Bi7 cuboctahedra,  a faceface with one Ba(3)Sn11Bi cuboctahedra, faces with three equivalent Ba(1)Sn7Bi5 cuboctahedra, and faces with three equivalent Ba(4)Sn9Bi3 cuboctahedra. In the third Ba site, Ba(3) is bonded to one Sn(1), two equivalent Sn(2), two equivalent Sn(3), two equivalent Sn(5), four equivalent Sn(4), and one Bi(1) atom to form distorted BaSn11Bi cuboctahedra that share corners with three equivalent Ba(2)Sn5Bi7 cuboctahedra, corners with six equivalent Ba(3)Sn11Bi cuboctahedra,  a faceface with one Ba(2)Sn5Bi7 cuboctahedra, faces with three equivalent Ba(1)Sn7Bi5 cuboctahedra, and faces with three equivalent Ba(4)Sn9Bi3 cuboctahedra. In the fourth Ba site, Ba(4) is bonded to one Sn(3), two equivalent Sn(1), two equivalent Sn(4), four equivalent Sn(2), one Bi(3), and two equivalent Bi(2) atoms to form distorted BaSn9Bi3 cuboctahedra that share corners with three equivalent Ba(1)Sn7Bi5 cuboctahedra, corners with six equivalent Ba(4)Sn9Bi3 cuboctahedra,  a faceface with one Ba(1)Sn7Bi5 cuboctahedra, faces with three equivalent Ba(3)Sn11Bi cuboctahedra, and faces with three equivalent Ba(2)Sn5Bi7 cuboctahedra. There are five 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(4), two equivalent Sn(2), two equivalent Sn(4), and two equivalent Bi(2) atoms. In the second Sn site, Sn(2) is bonded in a 10-coordinate geometry to one Ba(2), one Ba(3), two equivalent Ba(4), one Sn(1), one Sn(2), one Sn(3), one Sn(4), one Bi(2), and one Bi(3) atom. In the third Sn site, Sn(3) is bonded in a 10-coordinate geometry to one Ba(1), one Ba(4), two equivalent Ba(3), two equivalent Sn(2), two equivalent Sn(4), and two equivalent Sn(5) atoms. In the fourth Sn site, Sn(4) is bonded in a 10-coordinate geometry to one Ba(1), one Ba(4), two equivalent Ba(3), one Sn(1), one Sn(2), one Sn(3), one Sn(4), one Sn(5), and one Bi(1) atom. In the fifth Sn site, Sn(5) is bonded in a 4-coordinate geometry to one Ba(2), one Ba(3), two equivalent Ba(1), one Sn(3), and one Sn(4) atom. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a distorted square co-planar geometry to one Ba(2), one Ba(3), two equivalent Ba(1), and two equivalent Sn(4) atoms. In the second Bi site, Bi(2) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(4), two equivalent Ba(2), one Sn(1), and one Sn(2) atom. In the third Bi site, Bi(3) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(4), two equivalent Ba(2), and two equivalent Sn(2) atoms.
BaSn2Bi crystallizes in the monoclinic Cm space group. There are four inequivalent Ba sites. In the first Ba site, Ba(1) is bonded to one Sn(3), two equivalent Sn(4), four equivalent Sn(5), one Bi(3), two equivalent Bi(1), and two equivalent Bi(2) atoms to form BaSn7Bi5 cuboctahedra that share corners with three equivalent Ba(4)Sn9Bi3 cuboctahedra, corners with six equivalent Ba(1)Sn7Bi5 cuboctahedra,  a faceface with one Ba(4)Sn9Bi3 cuboctahedra, faces with three equivalent Ba(3)Sn11Bi cuboctahedra, and faces with three equivalent Ba(2)Sn5Bi7 cuboctahedra. The Ba(1)-Sn(3) bond length is 3.64 Å. Both Ba(1)-Sn(4) bond lengths are 3.66 Å. There are two shorter (3.64 Å) and two longer (3.68 Å) Ba(1)-Sn(5) bond lengths. The Ba(1)-Bi(3) bond length is 3.69 Å. Both Ba(1)-Bi(1) bond lengths are 3.66 Å. Both Ba(1)-Bi(2) bond lengths are 3.71 Å. In the second Ba site, Ba(2) is bonded to one Sn(1), two equivalent Sn(2), two equivalent Sn(5), one Bi(1), two equivalent Bi(3), and four equivalent Bi(2) atoms to form BaSn5Bi7 cuboctahedra that share corners with three equivalent Ba(3)Sn11Bi cuboctahedra, corners with six equivalent Ba(2)Sn5Bi7 cuboctahedra,  a faceface with one Ba(3)Sn11Bi cuboctahedra, faces with three equivalent Ba(1)Sn7Bi5 cuboctahedra, and faces with three equivalent Ba(4)Sn9Bi3 cuboctahedra. The Ba(2)-Sn(1) bond length is 3.67 Å. Both Ba(2)-Sn(2) bond lengths are 3.66 Å. Both Ba(2)-Sn(5) bond lengths are 3.74 Å. The Ba(2)-Bi(1) bond length is 3.72 Å. Both Ba(2)-Bi(3) bond lengths are 3.66 Å. There are two shorter (3.65 Å) and two longer (3.67 Å) Ba(2)-Bi(2) bond lengths. In the third Ba site, Ba(3) is bonded to one Sn(1), two equivalent Sn(2), two equivalent Sn(3), two equivalent Sn(5), four equivalent Sn(4), and one Bi(1) atom to form distorted BaSn11Bi cuboctahedra that share corners with three equivalent Ba(2)Sn5Bi7 cuboctahedra, corners with six equivalent Ba(3)Sn11Bi cuboctahedra,  a faceface with one Ba(2)Sn5Bi7 cuboctahedra, faces with three equivalent Ba(1)Sn7Bi5 cuboctahedra, and faces with three equivalent Ba(4)Sn9Bi3 cuboctahedra. The Ba(3)-Sn(1) bond length is 3.66 Å. Both Ba(3)-Sn(2) bond lengths are 3.66 Å. Both Ba(3)-Sn(3) bond lengths are 3.68 Å. Both Ba(3)-Sn(5) bond lengths are 3.66 Å. There are two shorter (3.66 Å) and two longer (3.69 Å) Ba(3)-Sn(4) bond lengths. The Ba(3)-Bi(1) bond length is 3.67 Å. In the fourth Ba site, Ba(4) is bonded to one Sn(3), two equivalent Sn(1), two equivalent Sn(4), four equivalent Sn(2), one Bi(3), and two equivalent Bi(2) atoms to form distorted BaSn9Bi3 cuboctahedra that share corners with three equivalent Ba(1)Sn7Bi5 cuboctahedra, corners with six equivalent Ba(4)Sn9Bi3 cuboctahedra,  a faceface with one Ba(1)Sn7Bi5 cuboctahedra, faces with three equivalent Ba(3)Sn11Bi cuboctahedra, and faces with three equivalent Ba(2)Sn5Bi7 cuboctahedra. The Ba(4)-Sn(3) bond length is 3.71 Å. Both Ba(4)-Sn(1) bond lengths are 3.67 Å. Both Ba(4)-Sn(4) bond lengths are 3.69 Å. There are two shorter (3.67 Å) and two longer (3.68 Å) Ba(4)-Sn(2) bond lengths. The Ba(4)-Bi(3) bond length is 3.69 Å. Both Ba(4)-Bi(2) bond lengths are 3.67 Å. There are five 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(4), two equivalent Sn(2), two equivalent Sn(4), and two equivalent Bi(2) atoms. Both Sn(1)-Sn(2) bond lengths are 3.04 Å. Both Sn(1)-Sn(4) bond lengths are 3.35 Å. Both Sn(1)-Bi(2) bond lengths are 3.50 Å. In the second Sn site, Sn(2) is bonded in a 10-coordinate geometry to one Ba(2), one Ba(3), two equivalent Ba(4), one Sn(1), one Sn(2), one Sn(3), one Sn(4), one Bi(2), and one Bi(3) atom. The Sn(2)-Sn(2) bond length is 3.02 Å. The Sn(2)-Sn(3) bond length is 3.37 Å. The Sn(2)-Sn(4) bond length is 3.34 Å. The Sn(2)-Bi(2) bond length is 3.50 Å. The Sn(2)-Bi(3) bond length is 3.56 Å. In the third Sn site, Sn(3) is bonded in a 10-coordinate geometry to one Ba(1), one Ba(4), two equivalent Ba(3), two equivalent Sn(2), two equivalent Sn(4), and two equivalent Sn(5) atoms. Both Sn(3)-Sn(4) bond lengths are 3.02 Å. Both Sn(3)-Sn(5) bond lengths are 3.46 Å. In the fourth Sn site, Sn(4) is bonded in a 10-coordinate geometry to one Ba(1), one Ba(4), two equivalent Ba(3), one Sn(1), one Sn(2), one Sn(3), one Sn(4), one Sn(5), and one Bi(1) atom. The Sn(4)-Sn(4) bond length is 3.03 Å. The Sn(4)-Sn(5) bond length is 3.47 Å. The Sn(4)-Bi(1) bond length is 3.51 Å. In the fifth Sn site, Sn(5) is bonded in a 4-coordinate geometry to one Ba(2), one Ba(3), two equivalent Ba(1), one Sn(3), and one Sn(4) atom. There are three inequivalent Bi sites. In the first Bi site, Bi(1) is bonded in a distorted square co-planar geometry to one Ba(2), one Ba(3), two equivalent Ba(1), and two equivalent Sn(4) atoms. In the second Bi site, Bi(2) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(4), two equivalent Ba(2), one Sn(1), and one Sn(2) atom. In the third Bi site, Bi(3) is bonded in a 4-coordinate geometry to one Ba(1), one Ba(4), two equivalent Ba(2), and two equivalent Sn(2) atoms.