Tl5Te3 crystallizes in the tetragonal I4/mcm space group. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 3-coordinate geometry to three equivalent Te(1) atoms. In the second Tl site, Tl(2) is bonded to two equivalent Te(2) and four equivalent Te(1) atoms to form corner-sharing TlTe6 octahedra. The corner-sharing octahedral tilt angles range from 0-40°. There are two inequivalent Te sites. In the first Te site, Te(2) is bonded in a linear geometry to two equivalent Tl(2) atoms. In the second Te site, Te(1) is bonded in a 8-coordinate geometry to two equivalent Tl(2) and six equivalent Tl(1) atoms.
Tl5Te3 crystallizes in the tetragonal I4/mcm space group. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded in a 3-coordinate geometry to three equivalent Te(1) atoms. There is one shorter (3.19 Å) and two longer (3.44 Å) Tl(1)-Te(1) bond lengths. In the second Tl site, Tl(2) is bonded to two equivalent Te(2) and four equivalent Te(1) atoms to form corner-sharing TlTe6 octahedra. The corner-sharing octahedral tilt angles range from 0-40°. Both Tl(2)-Te(2) bond lengths are 3.21 Å. All Tl(2)-Te(1) bond lengths are 3.41 Å. There are two inequivalent Te sites. In the first Te site, Te(2) is bonded in a linear geometry to two equivalent Tl(2) atoms. In the second Te site, Te(1) is bonded in a 8-coordinate geometry to two equivalent Tl(2) and six equivalent Tl(1) atoms.