Cu3P4(SBr)3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one P(1), one Br(2), and two equivalent Br(1) atoms to form corner-sharing CuPBr3 tetrahedra. In the second Cu site, Cu(2) is bonded to one P(2), one Br(2), and two equivalent Br(1) atoms to form corner-sharing CuPBr3 tetrahedra. There are three inequivalent P sites. In the first P site, P(1) is bonded in a tetrahedral geometry to one Cu(1), one S(1), and two equivalent S(2) atoms. In the second P site, P(2) is bonded in a distorted bent 120 degrees geometry to one Cu(2), one P(2), one P(3), and one S(2) atom. In the third P site, P(3) is bonded in a distorted single-bond geometry to two equivalent P(2) and one S(1) atom. There are two inequivalent S sites. In the first S site, S(2) is bonded in a water-like geometry to one P(1) and one P(2) atom. In the second S site, S(1) is bonded in a water-like geometry to one P(1) and one P(3) atom. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a trigonal non-coplanar geometry to one Cu(1) and two equivalent Cu(2) atoms. In the second Br site, Br(2) is bonded in a trigonal non-coplanar geometry to one Cu(1) and two equivalent Cu(2) atoms.
Cu3P4(SBr)3 crystallizes in the orthorhombic Pnma space group. There are two inequivalent Cu sites. In the first Cu site, Cu(1) is bonded to one P(1), one Br(2), and two equivalent Br(1) atoms to form corner-sharing CuPBr3 tetrahedra. The Cu(1)-P(1) bond length is 2.20 Å. The Cu(1)-Br(2) bond length is 2.46 Å. Both Cu(1)-Br(1) bond lengths are 2.51 Å. In the second Cu site, Cu(2) is bonded to one P(2), one Br(2), and two equivalent Br(1) atoms to form corner-sharing CuPBr3 tetrahedra. The Cu(2)-P(2) bond length is 2.22 Å. The Cu(2)-Br(2) bond length is 2.52 Å. There is one shorter (2.48 Å) and one longer (2.54 Å) Cu(2)-Br(1) bond length. There are three inequivalent P sites. In the first P site, P(1) is bonded in a tetrahedral geometry to one Cu(1), one S(1), and two equivalent S(2) atoms. The P(1)-S(1) bond length is 2.13 Å. Both P(1)-S(2) bond lengths are 2.12 Å. In the second P site, P(2) is bonded in a distorted bent 120 degrees geometry to one Cu(2), one P(2), one P(3), and one S(2) atom. The P(2)-P(2) bond length is 2.30 Å. The P(2)-P(3) bond length is 2.26 Å. The P(2)-S(2) bond length is 2.10 Å. In the third P site, P(3) is bonded in a distorted single-bond geometry to two equivalent P(2) and one S(1) atom. The P(3)-S(1) bond length is 2.10 Å. There are two inequivalent S sites. In the first S site, S(2) is bonded in a water-like geometry to one P(1) and one P(2) atom. In the second S site, S(1) is bonded in a water-like geometry to one P(1) and one P(3) atom. There are two inequivalent Br sites. In the first Br site, Br(1) is bonded in a trigonal non-coplanar geometry to one Cu(1) and two equivalent Cu(2) atoms. In the second Br site, Br(2) is bonded in a trigonal non-coplanar geometry to one Cu(1) and two equivalent Cu(2) atoms.