Template-Assisted Solvothermal Synthesis of Five Copper(I)−Thioantimonate(III) Composites: Crystal Structures and Optical and Thermal Properties of (C6N2H18)0.5Cu2SbS3, (C4N3H15)0.5Cu2SbS3, (C8N4H22)0.5Cu2SbS3, (C4N3H14)Cu3Sb2S5, and (C6N4H20)0.5Cu3Sb2S5

Abstract

The novel copper(I)-thioantimonates(III) (C(6)N(2)H(18))(0.5)Cu(2)SbS(3) (I) (C(6)N(2)H(16) = 1,6-diaminohexane), (C(4)N(3)H(15))(0.5)Cu(2)SbS(3) (II) (C(4)N(3)H(13) = diethylenetriamine), (C(8)N(4)H(22))(0.5)Cu(2)SbS(3) (III) (C(8)N(4)H(20) = 1,4-bis(2-aminoethyl)piperazine), (C(4)N(3)H(14))Cu(3)Sb(2)S(5) (IV) (C(4)N(3)H(13) = diethylenetriamine), and (C(6)N(4)H(20))(0.5)Cu(3)Sb(2)S(5) (V) (C(6)N(4)H(18) = triethylenetetramine) were synthesized under solvothermal conditions reacting Sb, Cu, and S with the amines. The compounds I-III belong to the RCu(2)SbS(3) structure family (R = amine) and are built up of trigonal SbS(3) pyramids and two CuS(3) moieties forming 6-membered (6 MR) and 10-membered (10 MR) rings. The rings are condensed yielding single layers which are joined into [Cu(2)SbS(3)](-) double layers via Cu-S bonds. The organic ions are located between the anionic layers, and the shortest interlayer distances are 7.8 Angstroms (I), 7.4 Angstroms (II), and 8.8 Angstroms (III). The structure of the novel inorganic-organic hybrid compound IV contains one SbS(3) group, one SbS(4) unit, two CuS(3) triangles, and one CuS(4) tetrahedron. These units are joined into four-membered (4 MR) and six-membered rings (6 MR) forming a hitherto unknown strong undulated layered (Cu(3)Sb(2)S(5))(-) anion. Anions and cations are arranged in a sandwichlike manner with an interlayer distance of 6.184 A. The new composite V contains an anion with the same chemical composition as compound IV, but the structure exhibits a unique and different network topology which is constructed by two SbS(3) pyramids, two CuS(3) triangles, and one CuS(4) tetrahedron. These units are joined into 6 MR which may be described as an inorganic graphene-like layer or as a 6(3) net. Two such layers are connected via Cu-S bonds into the final double layer. The interlayer distance amounts to 6.44 Angstroms. All compounds decompose in a more or less complex manner when heated in an inert atmosphere.