TlTaS3 crystallizes in the orthorhombic Pnma space group. Ta(1) is bonded to one S(2), two equivalent S(3), and three equivalent S(1) atoms to form distorted edge-sharing TaS6 octahedra. Tl(1) is bonded in a 5-coordinate geometry to one S(3) and four equivalent S(2) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to three equivalent Ta(1) atoms. In the second S site, S(2) is bonded in a distorted single-bond geometry to one Ta(1) and four equivalent Tl(1) atoms. In the third S site, S(3) is bonded in a distorted L-shaped geometry to two equivalent Ta(1) and one Tl(1) atom.
TlTaS3 crystallizes in the orthorhombic Pnma space group. Ta(1) is bonded to one S(2), two equivalent S(3), and three equivalent S(1) atoms to form distorted edge-sharing TaS6 octahedra. The Ta(1)-S(2) bond length is 2.24 Å. Both Ta(1)-S(3) bond lengths are 2.45 Å. There are two shorter (2.48 Å) and one longer (2.76 Å) Ta(1)-S(1) bond length. Tl(1) is bonded in a 5-coordinate geometry to one S(3) and four equivalent S(2) atoms. The Tl(1)-S(3) bond length is 3.20 Å. There are two shorter (3.13 Å) and two longer (3.24 Å) Tl(1)-S(2) bond lengths. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 3-coordinate geometry to three equivalent Ta(1) atoms. In the second S site, S(2) is bonded in a distorted single-bond geometry to one Ta(1) and four equivalent Tl(1) atoms. In the third S site, S(3) is bonded in a distorted L-shaped geometry to two equivalent Ta(1) and one Tl(1) atom.