Tl2BiSbTe4 is Caswellsilverite-derived structured and crystallizes in the monoclinic P2/m space group. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded to two equivalent Te(2) and four equivalent Te(1) atoms to form TlTe6 octahedra that share corners with six equivalent Bi(1)Te6 octahedra, edges with two equivalent Tl(1)Te6 octahedra, edges with two equivalent Bi(1)Te6 octahedra, edges with four equivalent Tl(2)Te6 octahedra, and edges with four equivalent Sb(1)Te6 octahedra. The corner-sharing octahedral tilt angles are 8°. In the second Tl site, Tl(2) is bonded to two equivalent Te(1) and four equivalent Te(2) atoms to form TlTe6 octahedra that share corners with six equivalent Sb(1)Te6 octahedra, edges with two equivalent Tl(2)Te6 octahedra, edges with two equivalent Sb(1)Te6 octahedra, edges with four equivalent Tl(1)Te6 octahedra, and edges with four equivalent Bi(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. Bi(1) is bonded to two equivalent Te(2) and four equivalent Te(1) atoms to form BiTe6 octahedra that share corners with six equivalent Tl(1)Te6 octahedra, edges with two equivalent Tl(1)Te6 octahedra, edges with two equivalent Bi(1)Te6 octahedra, edges with four equivalent Tl(2)Te6 octahedra, and edges with four equivalent Sb(1)Te6 octahedra. The corner-sharing octahedral tilt angles are 8°. Sb(1) is bonded to two equivalent Te(1) and four equivalent Te(2) atoms to form SbTe6 octahedra that share corners with six equivalent Tl(2)Te6 octahedra, edges with two equivalent Tl(2)Te6 octahedra, edges with two equivalent Sb(1)Te6 octahedra, edges with four equivalent Tl(1)Te6 octahedra, and edges with four equivalent Bi(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded to one Tl(2), two equivalent Tl(1), two equivalent Bi(1), and one Sb(1) atom to form TeTl3Bi2Sb octahedra that share corners with six equivalent Te(1)Tl3Bi2Sb octahedra, edges with four equivalent Te(1)Tl3Bi2Sb octahedra, and edges with eight equivalent Te(2)Tl3BiSb2 octahedra. The corner-sharing octahedra are not tilted. In the second Te site, Te(2) is bonded to one Tl(1), two equivalent Tl(2), one Bi(1), and two equivalent Sb(1) atoms to form TeTl3BiSb2 octahedra that share corners with six equivalent Te(2)Tl3BiSb2 octahedra, edges with four equivalent Te(2)Tl3BiSb2 octahedra, and edges with eight equivalent Te(1)Tl3Bi2Sb octahedra. The corner-sharing octahedra are not tilted.
Tl2BiSbTe4 is Caswellsilverite-derived structured and crystallizes in the monoclinic P2/m space group. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded to two equivalent Te(2) and four equivalent Te(1) atoms to form TlTe6 octahedra that share corners with six equivalent Bi(1)Te6 octahedra, edges with two equivalent Tl(1)Te6 octahedra, edges with two equivalent Bi(1)Te6 octahedra, edges with four equivalent Tl(2)Te6 octahedra, and edges with four equivalent Sb(1)Te6 octahedra. The corner-sharing octahedral tilt angles are 8°. Both Tl(1)-Te(2) bond lengths are 3.45 Å. All Tl(1)-Te(1) bond lengths are 3.44 Å. In the second Tl site, Tl(2) is bonded to two equivalent Te(1) and four equivalent Te(2) atoms to form TlTe6 octahedra that share corners with six equivalent Sb(1)Te6 octahedra, edges with two equivalent Tl(2)Te6 octahedra, edges with two equivalent Sb(1)Te6 octahedra, edges with four equivalent Tl(1)Te6 octahedra, and edges with four equivalent Bi(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. Both Tl(2)-Te(1) bond lengths are 3.50 Å. All Tl(2)-Te(2) bond lengths are 3.48 Å. Bi(1) is bonded to two equivalent Te(2) and four equivalent Te(1) atoms to form BiTe6 octahedra that share corners with six equivalent Tl(1)Te6 octahedra, edges with two equivalent Tl(1)Te6 octahedra, edges with two equivalent Bi(1)Te6 octahedra, edges with four equivalent Tl(2)Te6 octahedra, and edges with four equivalent Sb(1)Te6 octahedra. The corner-sharing octahedral tilt angles are 8°. Both Bi(1)-Te(2) bond lengths are 3.18 Å. All Bi(1)-Te(1) bond lengths are 3.17 Å. Sb(1) is bonded to two equivalent Te(1) and four equivalent Te(2) atoms to form SbTe6 octahedra that share corners with six equivalent Tl(2)Te6 octahedra, edges with two equivalent Tl(2)Te6 octahedra, edges with two equivalent Sb(1)Te6 octahedra, edges with four equivalent Tl(1)Te6 octahedra, and edges with four equivalent Bi(1)Te6 octahedra. The corner-sharing octahedral tilt angles range from 6-7°. Both Sb(1)-Te(1) bond lengths are 3.12 Å. All Sb(1)-Te(2) bond lengths are 3.13 Å. There are two inequivalent Te sites. In the first Te site, Te(1) is bonded to one Tl(2), two equivalent Tl(1), two equivalent Bi(1), and one Sb(1) atom to form TeTl3Bi2Sb octahedra that share corners with six equivalent Te(1)Tl3Bi2Sb octahedra, edges with four equivalent Te(1)Tl3Bi2Sb octahedra, and edges with eight equivalent Te(2)Tl3BiSb2 octahedra. The corner-sharing octahedra are not tilted. In the second Te site, Te(2) is bonded to one Tl(1), two equivalent Tl(2), one Bi(1), and two equivalent Sb(1) atoms to form TeTl3BiSb2 octahedra that share corners with six equivalent Te(2)Tl3BiSb2 octahedra, edges with four equivalent Te(2)Tl3BiSb2 octahedra, and edges with eight equivalent Te(1)Tl3Bi2Sb octahedra. The corner-sharing octahedra are not tilted.