TlPbAs3S6 crystallizes in the orthorhombic Fdd2 space group. The structure consists of sixteen 7440-28-0 atoms inside a PbAs3S6 framework. In the PbAs3S6 framework, Pb(1) is bonded to one S(6), two equivalent S(2), and two equivalent S(3) atoms to form edge-sharing PbS5 square pyramids. There are three inequivalent As sites. In the first As site, As(1) is bonded in a distorted T-shaped geometry to one S(5) and two equivalent S(4) atoms. In the second As site, As(2) is bonded in a trigonal non-coplanar geometry to one S(1), one S(2), and one S(6) atom. In the third As site, As(3) is bonded in a 3-coordinate geometry to one S(1), one S(3), and one S(5) atom. There are six inequivalent S sites. In the first S site, S(1) is bonded in an L-shaped geometry to one As(2) and one As(3) atom. In the second S site, S(2) is bonded in a 1-coordinate geometry to two equivalent Pb(1) and one As(2) atom. In the third S site, S(3) is bonded in a 1-coordinate geometry to two equivalent Pb(1) and one As(3) atom. In the fourth S site, S(4) is bonded in a distorted L-shaped geometry to two equivalent As(1) atoms. In the fifth S site, S(5) is bonded in a water-like geometry to one As(1) and one As(3) atom. In the sixth S site, S(6) is bonded in a distorted L-shaped geometry to one Pb(1) and one As(2) atom.
TlPbAs3S6 crystallizes in the orthorhombic Fdd2 space group. The structure consists of sixteen 7440-28-0 atoms inside a PbAs3S6 framework. In the PbAs3S6 framework, Pb(1) is bonded to one S(6), two equivalent S(2), and two equivalent S(3) atoms to form edge-sharing PbS5 square pyramids. The Pb(1)-S(6) bond length is 2.82 Å. There is one shorter (2.95 Å) and one longer (3.06 Å) Pb(1)-S(2) bond length. There is one shorter (2.95 Å) and one longer (3.10 Å) Pb(1)-S(3) bond length. There are three inequivalent As sites. In the first As site, As(1) is bonded in a distorted T-shaped geometry to one S(5) and two equivalent S(4) atoms. The As(1)-S(5) bond length is 2.28 Å. There is one shorter (2.32 Å) and one longer (2.37 Å) As(1)-S(4) bond length. In the second As site, As(2) is bonded in a trigonal non-coplanar geometry to one S(1), one S(2), and one S(6) atom. The As(2)-S(1) bond length is 2.36 Å. The As(2)-S(2) bond length is 2.26 Å. The As(2)-S(6) bond length is 2.27 Å. In the third As site, As(3) is bonded in a 3-coordinate geometry to one S(1), one S(3), and one S(5) atom. The As(3)-S(1) bond length is 2.33 Å. The As(3)-S(3) bond length is 2.25 Å. The As(3)-S(5) bond length is 2.35 Å. There are six inequivalent S sites. In the first S site, S(1) is bonded in an L-shaped geometry to one As(2) and one As(3) atom. In the second S site, S(2) is bonded in a 1-coordinate geometry to two equivalent Pb(1) and one As(2) atom. In the third S site, S(3) is bonded in a 1-coordinate geometry to two equivalent Pb(1) and one As(3) atom. In the fourth S site, S(4) is bonded in a distorted L-shaped geometry to two equivalent As(1) atoms. In the fifth S site, S(5) is bonded in a water-like geometry to one As(1) and one As(3) atom. In the sixth S site, S(6) is bonded in a distorted L-shaped geometry to one Pb(1) and one As(2) atom.