Cu3SbS3 crystallizes in the orthorhombic P2_12_12_1 space group. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 3-coordinate geometry to one S(2), one S(3), and two equivalent S(1) atoms. In the second Cu site, Cu(2) is bonded in a distorted trigonal planar geometry to one S(2) and two equivalent S(1) atoms. In the third Cu site, Cu(3) is bonded in a trigonal planar geometry to one S(2) and two equivalent S(3) atoms. Sb(1) is bonded in a distorted trigonal non-coplanar geometry to one S(1), one S(2), and one S(3) atom. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Cu(1), two equivalent Cu(2), and one Sb(1) atom. In the second S site, S(2) is bonded to one Cu(1), one Cu(2), one Cu(3), and one Sb(1) atom to form distorted corner-sharing SCu3Sb trigonal pyramids. In the third S site, S(3) is bonded to one Cu(1), two equivalent Cu(3), and one Sb(1) atom to form distorted corner-sharing SCu3Sb tetrahedra.
Cu3SbS3 crystallizes in the orthorhombic P2_12_12_1 space group. There are three inequivalent Cu sites. In the first Cu site, Cu(1) is bonded in a 3-coordinate geometry to one S(2), one S(3), and two equivalent S(1) atoms. The Cu(1)-S(2) bond length is 2.31 Å. The Cu(1)-S(3) bond length is 2.26 Å. There is one shorter (2.32 Å) and one longer (2.85 Å) Cu(1)-S(1) bond length. In the second Cu site, Cu(2) is bonded in a distorted trigonal planar geometry to one S(2) and two equivalent S(1) atoms. The Cu(2)-S(2) bond length is 2.26 Å. There is one shorter (2.28 Å) and one longer (2.31 Å) Cu(2)-S(1) bond length. In the third Cu site, Cu(3) is bonded in a trigonal planar geometry to one S(2) and two equivalent S(3) atoms. The Cu(3)-S(2) bond length is 2.24 Å. There is one shorter (2.28 Å) and one longer (2.30 Å) Cu(3)-S(3) bond length. Sb(1) is bonded in a distorted trigonal non-coplanar geometry to one S(1), one S(2), and one S(3) atom. The Sb(1)-S(1) bond length is 2.52 Å. The Sb(1)-S(2) bond length is 2.51 Å. The Sb(1)-S(3) bond length is 2.51 Å. There are three inequivalent S sites. In the first S site, S(1) is bonded in a 5-coordinate geometry to two equivalent Cu(1), two equivalent Cu(2), and one Sb(1) atom. In the second S site, S(2) is bonded to one Cu(1), one Cu(2), one Cu(3), and one Sb(1) atom to form distorted corner-sharing SCu3Sb trigonal pyramids. In the third S site, S(3) is bonded to one Cu(1), two equivalent Cu(3), and one Sb(1) atom to form distorted corner-sharing SCu3Sb tetrahedra.