Cu3SbSe3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent Se(1) and two equivalent Se(2) atoms to form distorted corner-sharing CuSe4 tetrahedra. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to one Se(2) and three equivalent Se(1) atoms. Sb(1) is bonded in a distorted trigonal non-coplanar geometry to one Se(2) and two equivalent Se(1) atoms. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded in a 5-coordinate geometry to one Cu(1), three equivalent Cu(2), and one Sb(1) atom. In the second Se site, Se(2) is bonded to two equivalent Cu(1), two equivalent Cu(2), and one Sb(1) atom to form distorted corner-sharing SeCu4Sb trigonal bipyramids.
Cu3SbSe3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to two equivalent Se(1) and two equivalent Se(2) atoms to form distorted corner-sharing CuSe4 tetrahedra. Both Cu(1)-Se(1) bond lengths are 2.51 Å. There is one shorter (2.52 Å) and one longer (2.55 Å) Cu(1)-Se(2) bond length. In the second Cu site, Cu(2) is bonded in a 4-coordinate geometry to one Se(2) and three equivalent Se(1) atoms. The Cu(2)-Se(2) bond length is 2.43 Å. There are a spread of Cu(2)-Se(1) bond distances ranging from 2.39-2.79 Å. Sb(1) is bonded in a distorted trigonal non-coplanar geometry to one Se(2) and two equivalent Se(1) atoms. The Sb(1)-Se(2) bond length is 2.63 Å. Both Sb(1)-Se(1) bond lengths are 2.68 Å. There are two inequivalent Se sites. In the first Se site, Se(1) is bonded in a 5-coordinate geometry to one Cu(1), three equivalent Cu(2), and one Sb(1) atom. In the second Se site, Se(2) is bonded to two equivalent Cu(1), two equivalent Cu(2), and one Sb(1) atom to form distorted corner-sharing SeCu4Sb trigonal bipyramids.