Sc2Cu3TlS5 crystallizes in the orthorhombic Cmcm space group. Sc(1) is bonded to one S(1), two equivalent S(3), and three equivalent S(2) atoms to form ScS6 octahedra that share  a cornercorner with one Sc(1)S6 octahedra, corners with four equivalent Cu(1)S4 tetrahedra, edges with four equivalent Sc(1)S6 octahedra, edges with two equivalent Cu(2)S4 tetrahedra, and edges with three equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 31°. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent S(2) and two equivalent S(3) atoms to form distorted CuS4 tetrahedra that share corners with four equivalent Sc(1)S6 octahedra, corners with two equivalent Cu(1)S4 tetrahedra, corners with two equivalent Cu(2)S4 tetrahedra, edges with three equivalent Sc(1)S6 octahedra, and  an edgeedge with one Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 11-57°. In the second Cu site, Cu(2) is bonded to two equivalent S(1) and two equivalent S(3) atoms to form CuS4 tetrahedra that share corners with two equivalent Cu(2)S4 tetrahedra, corners with four equivalent Cu(1)S4 tetrahedra, and edges with four equivalent Sc(1)S6 octahedra. Tl(1) is bonded in a 4-coordinate geometry to two equivalent S(1) and two equivalent S(2) atoms. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to two equivalent Sc(1), two equivalent Cu(2), and two equivalent Tl(1) atoms. In the second S site, S(2) is bonded to three equivalent Sc(1), two equivalent Cu(1), and one Tl(1) atom to form a mixture of distorted corner and edge-sharing SSc3TlCu2 square pyramids. In the third S site, S(3) is bonded in a distorted pentagonal planar geometry to two equivalent Sc(1), one Cu(2), and two equivalent Cu(1) atoms.
Sc2Cu3TlS5 crystallizes in the orthorhombic Cmcm space group. Sc(1) is bonded to one S(1), two equivalent S(3), and three equivalent S(2) atoms to form ScS6 octahedra that share  a cornercorner with one Sc(1)S6 octahedra, corners with four equivalent Cu(1)S4 tetrahedra, edges with four equivalent Sc(1)S6 octahedra, edges with two equivalent Cu(2)S4 tetrahedra, and edges with three equivalent Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles are 31°. The Sc(1)-S(1) bond length is 2.54 Å. Both Sc(1)-S(3) bond lengths are 2.60 Å. There is one shorter (2.59 Å) and two longer (2.67 Å) Sc(1)-S(2) bond lengths. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent S(2) and two equivalent S(3) atoms to form distorted CuS4 tetrahedra that share corners with four equivalent Sc(1)S6 octahedra, corners with two equivalent Cu(1)S4 tetrahedra, corners with two equivalent Cu(2)S4 tetrahedra, edges with three equivalent Sc(1)S6 octahedra, and  an edgeedge with one Cu(1)S4 tetrahedra. The corner-sharing octahedral tilt angles range from 11-57°. Both Cu(1)-S(2) bond lengths are 2.31 Å. There is one shorter (2.31 Å) and one longer (2.48 Å) Cu(1)-S(3) bond length. In the second Cu site, Cu(2) is bonded to two equivalent S(1) and two equivalent S(3) atoms to form CuS4 tetrahedra that share corners with two equivalent Cu(2)S4 tetrahedra, corners with four equivalent Cu(1)S4 tetrahedra, and edges with four equivalent Sc(1)S6 octahedra. Both Cu(2)-S(1) bond lengths are 2.32 Å. Both Cu(2)-S(3) bond lengths are 2.42 Å. Tl(1) is bonded in a 4-coordinate geometry to two equivalent S(1) and two equivalent S(2) atoms. Both Tl(1)-S(1) bond lengths are 3.21 Å. Both Tl(1)-S(2) bond lengths are 3.19 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 4-coordinate geometry to two equivalent Sc(1), two equivalent Cu(2), and two equivalent Tl(1) atoms. In the second S site, S(2) is bonded to three equivalent Sc(1), two equivalent Cu(1), and one Tl(1) atom to form a mixture of distorted corner and edge-sharing SSc3TlCu2 square pyramids. In the third S site, S(3) is bonded in a distorted pentagonal planar geometry to two equivalent Sc(1), one Cu(2), and two equivalent Cu(1) atoms.