Tl4Sn crystallizes in the trigonal R-3m space group. There are six inequivalent Tl sites. In the first Tl site, Tl(1) is bonded to three equivalent Tl(2), six equivalent Tl(1), and three equivalent Sn(1) atoms to form distorted TlTl9Sn3 cuboctahedra that share corners with three equivalent Tl(2)Tl12 cuboctahedra; corners with nine equivalent Tl(1)Tl9Sn3 cuboctahedra; edges with nine Tl(2,2)Tl12 cuboctahedra; edges with nine equivalent Tl(1)Tl9Sn3 cuboctahedra; faces with six equivalent Tl(2)Tl12 cuboctahedra; and faces with six equivalent Tl(1)Tl9Sn3 cuboctahedra. In the second Tl site, Tl(2) is bonded to three equivalent Tl(1) and nine Tl(2,2) atoms to form TlTl12 cuboctahedra that share corners with three equivalent Tl(1)Tl9Sn3 cuboctahedra; corners with six equivalent Tl(2)Tl12 cuboctahedra; edges with nine equivalent Tl(1)Tl9Sn3 cuboctahedra; edges with twelve Tl(2,2)Tl12 cuboctahedra; faces with six equivalent Tl(1)Tl9Sn3 cuboctahedra; and faces with twelve Tl(2,2)Tl12 cuboctahedra. In the third Tl site, Tl(2) is bonded to three equivalent Tl(1) and nine Tl(2,2) atoms to form TlTl12 cuboctahedra that share corners with three equivalent Tl(1)Tl9Sn3 cuboctahedra; corners with six equivalent Tl(2)Tl12 cuboctahedra; edges with nine equivalent Tl(1)Tl9Sn3 cuboctahedra; edges with twelve Tl(2,2)Tl12 cuboctahedra; faces with six equivalent Tl(1)Tl9Sn3 cuboctahedra; and faces with twelve Tl(2,2)Tl12 cuboctahedra. In the fourth Tl site, Tl(2) is bonded to three equivalent Tl(1) and nine Tl(2,2) atoms to form TlTl12 cuboctahedra that share corners with three equivalent Tl(1)Tl9Sn3 cuboctahedra; corners with six equivalent Tl(2)Tl12 cuboctahedra; edges with nine equivalent Tl(1)Tl9Sn3 cuboctahedra; edges with twelve Tl(2,2)Tl12 cuboctahedra; faces with six equivalent Tl(1)Tl9Sn3 cuboctahedra; and faces with twelve Tl(2,2)Tl12 cuboctahedra. In the fifth Tl site, Tl(2) is bonded to three equivalent Tl(1) and nine Tl(2,2) atoms to form TlTl12 cuboctahedra that share corners with three equivalent Tl(1)Tl9Sn3 cuboctahedra; corners with six equivalent Tl(2)Tl12 cuboctahedra; edges with nine equivalent Tl(1)Tl9Sn3 cuboctahedra; edges with twelve Tl(2,2)Tl12 cuboctahedra; faces with six equivalent Tl(1)Tl9Sn3 cuboctahedra; and faces with twelve Tl(2,2)Tl12 cuboctahedra. In the sixth Tl site, Tl(2) is bonded to three equivalent Tl(1) and nine Tl(2,2) atoms to form TlTl12 cuboctahedra that share corners with three equivalent Tl(1)Tl9Sn3 cuboctahedra; corners with six equivalent Tl(2)Tl12 cuboctahedra; edges with nine equivalent Tl(1)Tl9Sn3 cuboctahedra; edges with twelve Tl(2,2)Tl12 cuboctahedra; faces with six equivalent Tl(1)Tl9Sn3 cuboctahedra; and faces with twelve Tl(2,2)Tl12 cuboctahedra. Sn(1) is bonded in a 6-coordinate geometry to six equivalent Tl(1) atoms.
Tl4Sn crystallizes in the trigonal R-3m space group. There are six inequivalent Tl sites. In the first Tl site, Tl(1) is bonded to three equivalent Tl(2), six equivalent Tl(1), and three equivalent Sn(1) atoms to form distorted TlTl9Sn3 cuboctahedra that share corners with three equivalent Tl(2)Tl12 cuboctahedra; corners with nine equivalent Tl(1)Tl9Sn3 cuboctahedra; edges with nine Tl(2,2)Tl12 cuboctahedra; edges with nine equivalent Tl(1)Tl9Sn3 cuboctahedra; faces with six equivalent Tl(2)Tl12 cuboctahedra; and faces with six equivalent Tl(1)Tl9Sn3 cuboctahedra. All Tl(1)-Tl(2) bond lengths are 3.51 Å. All Tl(1)-Tl(1) bond lengths are 3.47 Å. All Tl(1)-Sn(1) bond lengths are 3.39 Å. In the second Tl site, Tl(2) is bonded to three equivalent Tl(1) and nine Tl(2,2) atoms to form TlTl12 cuboctahedra that share corners with three equivalent Tl(1)Tl9Sn3 cuboctahedra; corners with six equivalent Tl(2)Tl12 cuboctahedra; edges with nine equivalent Tl(1)Tl9Sn3 cuboctahedra; edges with twelve Tl(2,2)Tl12 cuboctahedra; faces with six equivalent Tl(1)Tl9Sn3 cuboctahedra; and faces with twelve Tl(2,2)Tl12 cuboctahedra. There are six shorter (3.47 Å) and three longer (3.53 Å) Tl(2)-Tl(2,2) bond lengths. In the third Tl site, Tl(2) is bonded to three equivalent Tl(1) and nine Tl(2,2) atoms to form TlTl12 cuboctahedra that share corners with three equivalent Tl(1)Tl9Sn3 cuboctahedra; corners with six equivalent Tl(2)Tl12 cuboctahedra; edges with nine equivalent Tl(1)Tl9Sn3 cuboctahedra; edges with twelve Tl(2,2)Tl12 cuboctahedra; faces with six equivalent Tl(1)Tl9Sn3 cuboctahedra; and faces with twelve Tl(2,2)Tl12 cuboctahedra. All Tl(2)-Tl(1) bond lengths are 3.51 Å. All Tl(2)-Tl(2) bond lengths are 3.47 Å. In the fourth Tl site, Tl(2) is bonded to three equivalent Tl(1) and nine Tl(2,2) atoms to form TlTl12 cuboctahedra that share corners with three equivalent Tl(1)Tl9Sn3 cuboctahedra; corners with six equivalent Tl(2)Tl12 cuboctahedra; edges with nine equivalent Tl(1)Tl9Sn3 cuboctahedra; edges with twelve Tl(2,2)Tl12 cuboctahedra; faces with six equivalent Tl(1)Tl9Sn3 cuboctahedra; and faces with twelve Tl(2,2)Tl12 cuboctahedra. All Tl(2)-Tl(1) bond lengths are 3.51 Å. There are six shorter (3.47 Å) and three longer (3.53 Å) Tl(2)-Tl(2,2) bond lengths. In the fifth Tl site, Tl(2) is bonded to three equivalent Tl(1) and nine Tl(2,2) atoms to form TlTl12 cuboctahedra that share corners with three equivalent Tl(1)Tl9Sn3 cuboctahedra; corners with six equivalent Tl(2)Tl12 cuboctahedra; edges with nine equivalent Tl(1)Tl9Sn3 cuboctahedra; edges with twelve Tl(2,2)Tl12 cuboctahedra; faces with six equivalent Tl(1)Tl9Sn3 cuboctahedra; and faces with twelve Tl(2,2)Tl12 cuboctahedra. All Tl(2)-Tl(1) bond lengths are 3.51 Å. All Tl(2)-Tl(2) bond lengths are 3.47 Å. In the sixth Tl site, Tl(2) is bonded to three equivalent Tl(1) and nine Tl(2,2) atoms to form TlTl12 cuboctahedra that share corners with three equivalent Tl(1)Tl9Sn3 cuboctahedra; corners with six equivalent Tl(2)Tl12 cuboctahedra; edges with nine equivalent Tl(1)Tl9Sn3 cuboctahedra; edges with twelve Tl(2,2)Tl12 cuboctahedra; faces with six equivalent Tl(1)Tl9Sn3 cuboctahedra; and faces with twelve Tl(2,2)Tl12 cuboctahedra. All Tl(2)-Tl(1) bond lengths are 3.51 Å. There are six shorter (3.47 Å) and three longer (3.53 Å) Tl(2)-Tl(2,2) bond lengths. Sn(1) is bonded in a 6-coordinate geometry to six equivalent Tl(1) atoms.