Tl6SI4 crystallizes in the tetragonal P4/mnc space group. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded to one S(1) and four equivalent I(1) atoms to form a mixture of distorted face and corner-sharing TlSI4 square pyramids. In the second Tl site, Tl(2) is bonded to one S(1) and four equivalent I(1) atoms to form a mixture of distorted face and corner-sharing TlSI4 square pyramids. S(1) is bonded in an octahedral geometry to two equivalent Tl(2) and four equivalent Tl(1) atoms. I(1) is bonded in a 6-coordinate geometry to two equivalent Tl(2) and four equivalent Tl(1) atoms.
Tl6SI4 crystallizes in the tetragonal P4/mnc space group. There are two inequivalent Tl sites. In the first Tl site, Tl(1) is bonded to one S(1) and four equivalent I(1) atoms to form a mixture of distorted face and corner-sharing TlSI4 square pyramids. The Tl(1)-S(1) bond length is 3.00 Å. There are two shorter (3.52 Å) and two longer (3.53 Å) Tl(1)-I(1) bond lengths. In the second Tl site, Tl(2) is bonded to one S(1) and four equivalent I(1) atoms to form a mixture of distorted face and corner-sharing TlSI4 square pyramids. The Tl(2)-S(1) bond length is 2.90 Å. All Tl(2)-I(1) bond lengths are 3.51 Å. S(1) is bonded in an octahedral geometry to two equivalent Tl(2) and four equivalent Tl(1) atoms. I(1) is bonded in a 6-coordinate geometry to two equivalent Tl(2) and four equivalent Tl(1) atoms.