TlPbPS4 crystallizes in the orthorhombic Pnma space group. Tl(1) is bonded in a 2-coordinate geometry to two equivalent S(3) atoms. Pb(1) is bonded in a 6-coordinate geometry to one S(1), one S(2), and four equivalent S(3) atoms. P(1) is bonded in a tetrahedral geometry to one S(1), one S(2), and two equivalent S(3) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted L-shaped geometry to one Pb(1) and one P(1) atom. In the second S site, S(2) is bonded in a distorted L-shaped geometry to one Pb(1) and one P(1) atom. In the third S site, S(3) is bonded in a single-bond geometry to one Tl(1), two equivalent Pb(1), and one P(1) atom.
TlPbPS4 crystallizes in the orthorhombic Pnma space group. Tl(1) is bonded in a 2-coordinate geometry to two equivalent S(3) atoms. Both Tl(1)-S(3) bond lengths are 3.24 Å. Pb(1) is bonded in a 6-coordinate geometry to one S(1), one S(2), and four equivalent S(3) atoms. The Pb(1)-S(1) bond length is 2.87 Å. The Pb(1)-S(2) bond length is 2.95 Å. There are two shorter (3.14 Å) and two longer (3.20 Å) Pb(1)-S(3) bond lengths. P(1) is bonded in a tetrahedral geometry to one S(1), one S(2), and two equivalent S(3) atoms. The P(1)-S(1) bond length is 2.06 Å. The P(1)-S(2) bond length is 2.06 Å. Both P(1)-S(3) bond lengths are 2.05 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a distorted L-shaped geometry to one Pb(1) and one P(1) atom. In the second S site, S(2) is bonded in a distorted L-shaped geometry to one Pb(1) and one P(1) atom. In the third S site, S(3) is bonded in a single-bond geometry to one Tl(1), two equivalent Pb(1), and one P(1) atom.