The synthesis and characterisation of two new iron thioantimonates: [Fe(en)3]2Sb2S5 · 0.55H2O and [Fe(en)3]2Sb4S8

Two new iron thioantimonates, [Fe(en)3]2Sb2S5 · 0.55H2O (1) and [Fe(en)3]2Sb4S8 (2), were synthesised under solvothermal conditions from the reactions of Sb2S3, FeCl2 and S in the presence of ethylenediamine at 413 and 438 K, respectively. The products were characterised by single-crystal X-ray diffraction, elemental analysis and SQUID magnetometry. Compound 1 is unusual in containing isolated Sb2S54- anions formed from two corner-sharing SbS33- trigonal pyramids. These units are arranged in rippled layers, 4 Å apart, parallel to the bc-plane. Octahedrally coordinated [Fe(en)3]2+ cations lie in depressions within these anionic layers. In compound (2), repeated corner linking of SbS33- trigonal pyramids generatesSbS2- chains, which may be considered as a polymerised form of the Sb2S54- anions in 1. The SbS2- chains are separated by [Fe(en)3]2+ cations. In both compounds, there is an extensive network of hydrogen bonds between the nitrogen atoms of the ethylenediamine ligands and the sulfur atoms of the anions and, in the case of 1, the uncoordinated water molecule.

Graphical abstractThe iron thioantimonates, [Fe(en)3]2Sb2S5 · 0.55H2O (1) and [Fe(en)3]2Sb4S8 (2) have been prepared under solvothermal conditions. Compound 1 contains isolated Sb2S54- anions formed from two corner-sharing SbS33- trigonal pyramids, whereas in 2, repeated corner linking of the same SbS33- trigonal pyramids generates SbS2- chains.Figure optionsDownload full-size imageDownload as PowerPoint slide