Three new thioantimonate(III) complexes [Ni(1,2‐PDA)3]Sb4S7 (1) (1,2‐PDA = 1,2‐propanediamine), [dmenH22+]Sb8S13·H2O (2) (dmen = N,N‐dimethylethylenediamine), and [deenH22+]Sb10S16·H2O (3) (deen = N,N‐diethylethylenediamine), prepared under solvothermal conditions, have been characterized by single‐crystal X‐ray diffraction, elemental analysis, and DTA‐TG measurements. In compound 1, a rectangle‐like Sb16S16 heteroring whose dimensions are about 8.1 × 14.7 Å is observed, this is the largest reported pore in layered thioantimonates to date. Further condensation of the Sb16S16 heterorings resulted in an unprecedented framework of the five‐atom thick SbxSyn– layer. In 2, a new member of SbnSn (n = 2, 3, 4, 8, 16, 30, 31, 32) heterocycles Sb15S15 heteroring has been obtained as the first example. In compound 3, the most particular feature is that when the secondary Sb–S bonds are considered the Sb2 atom becomes sevenfold coordinated.(© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2007)

and [C6H18N2]Sb10S16·H2O. -The structures of the title compounds (IV) (monoclinic, space group P21/n, Z = 4). (V) (monoclinic, space group P21/c, Z = 4), and (VI) (monoclinic, space group P21/c, Z = 4) are determined by single crystal XRD. In compound (IV), a rectangle-like Sb16S16 heteroring is found. Its size of about 8.1 x 14.7 Å represents the largest pore reported so far for layered thioantimonates. Further condensation of the Sb16S16 ring results in an unprecedented framework of the five-atom thick Sbx layer. In (V), a new member of SbnSn (n = 2, 3, 4, 8, 16, 30, 31, 32) heterocycles, Sb15S15, is observed for the first time. Compound (VI) contains Sb30S30 rings. The most striking feature of this structure is that the Sb2 atom becomes sevenfold coordinated. -(ZHANG, M.; SHENG, T. L.; HUANG, X. H.; FU, R. B.; WANG, X.; HU, S. M.; XIANG, S. C.; WU*, X. T.; Eur.