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TlBi is Tetraauricupride structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Tl is bonded in a body-centered cubic geometry to eight equivalent Bi atoms. All Tl–Bi bond lengths are 3.46 Å. Bi is bonded in a body-centered cubic geometry to eight equivalent Tl atoms.
TlBi2 crystallizes in the hexagonal P6/mmm space group. The structure is three-dimensional. Tl is bonded in a 2-coordinate geometry to two equivalent Tl and twelve equivalent Bi atoms. Both Tl–Tl bond lengths are 3.45 Å. All Tl–Bi bond lengths are 3.72 Å. Bi is bonded to six equivalent Tl and five equivalent Bi atoms to form a mixture of distorted edge, face, and corner-sharing BiTl6Bi5 trigonal bipyramids. There are three shorter (3.30 Å) and two longer (3.45 Å) Bi–Bi bond lengths.
Tl4Bi is beta-derived structured and crystallizes in the trigonal R-3m space group. The structure is three-dimensional. there are two inequivalent Tl sites. In the first Tl site, Tl is bonded in a 12-coordinate geometry to nine Tl and three equivalent Bi atoms. There are six shorter (3.50 Å) and three longer (3.60 Å) Tl–Tl bond lengths. All Tl–Bi bond lengths are 3.59 Å. In the second Tl site, Tl is bonded to twelve Tl atoms to form TlTl12 cuboctahedra that share corners with three equivalent BiTl6Bi6 cuboctahedra, corners with six equivalent TlTl12 cuboctahedra, edges with three equivalent BiTl6Bi6 cuboctahedra, edges with twelve equivalent TlTl12 cuboctahedra, and faces with twelve equivalent TlTl12 cuboctahedra. There are six shorter (3.50 Å) and three longer (3.62 Å) Tl–Tl bond lengths. Bi is bonded to six equivalent Tl and six equivalent Bi atoms to form BiTl6Bi6 cuboctahedra that share corners with six equivalent TlTl12 cuboctahedra, corners with six equivalent BiTl6Bi6 cuboctahedra, edges with six equivalent TlTl12 cuboctahedra, edges with six equivalent BiTl6Bi6 cuboctahedra, and faces with six equivalent BiTl6Bi6 cuboctahedra. All Bi–Bi bond lengths are 3.50 Å.
Tl3Bi is Uranium Silicide structured and crystallizes in the cubic Pm-3m space group. The structure is three-dimensional. Tl is bonded to eight equivalent Tl and four equivalent Bi atoms to form distorted TlTl8Bi4 cuboctahedra that share corners with twelve equivalent TlTl8Bi4 cuboctahedra, edges with eight equivalent BiTl12 cuboctahedra, edges with sixteen equivalent TlTl8Bi4 cuboctahedra, faces with four equivalent BiTl12 cuboctahedra, and faces with fourteen equivalent TlTl8Bi4 cuboctahedra. All Tl–Tl bond lengths are 3.56 Å. All Tl–Bi bond lengths are 3.56 Å. Bi is bonded to twelve equivalent Tl atoms to form BiTl12 cuboctahedra that share corners with twelve equivalent BiTl12 cuboctahedra, edges with twenty-four equivalent TlTl8Bi4 cuboctahedra, faces with six equivalent BiTl12 cuboctahedra, and faces with twelve equivalent TlTl8Bi4 cuboctahedra.
Tl3Bi crystallizes in the hexagonal P-6m2 space group. The structure is three-dimensional. there are two inequivalent Tl sites. In the first Tl site, Tl is bonded to twelve Tl atoms to form TlTl12 cuboctahedra that share corners with twelve equivalent BiTl6Bi6 cuboctahedra, corners with eighteen TlTl12 cuboctahedra, edges with eighteen TlTl12 cuboctahedra, faces with two equivalent BiTl6Bi6 cuboctahedra, and faces with six equivalent TlTl12 cuboctahedra. There are six shorter (3.54 Å) and six longer (3.57 Å) Tl–Tl bond lengths. In the second Tl site, Tl is bonded to three equivalent Tl and three equivalent Bi atoms to form distorted TlTl3Bi3 cuboctahedra that share corners with six equivalent BiTl6Bi6 cuboctahedra, corners with eighteen TlTl12 cuboctahedra, edges with six equivalent BiTl6Bi6 cuboctahedra, edges with twelve TlTl12 cuboctahedra, and faces with two equivalent TlTl3Bi3 cuboctahedra. All Tl–Bi bond lengths are 3.54 Å. Bi is bonded to six equivalent Tl and six equivalent Bi atoms to form distorted BiTl6Bi6 cuboctahedra that share corners with six equivalent BiTl6Bi6 cuboctahedra, corners with twenty-four TlTl12 cuboctahedra, edges with six equivalent BiTl6Bi6 cuboctahedra, edges with twelve equivalent TlTl3Bi3 cuboctahedra, faces with two equivalent TlTl12 cuboctahedra, and faces with six equivalent BiTl6Bi6 cuboctahedra. All Bi–Bi bond lengths are 3.57 Å.