Synthesis and Structures of Compounds Based on Chalcocyanide Tetranuclear Rhenium Clusters: Bonding Cluster Complexes by diene‐Bridged CuIIUnits

Six new tetrahedral chalcocyanide cluster compounds, [{Cu2(dien)3}Re4S4(CN)12] (1), [{Cu(dien)(NH3)}2Re4Se4(CN)12]·2.5H2O (2), [{Cu2(dien)3}Re4Q4(CN)12]·nH2O (Q = Se (3), Te (4)] and [K(H2O)2]2[{Cu3(dien)4}{Re4Q4(CN)12}2]·8H2O where Q = Se (5), Te (6) (dien = diethylenetriamine), have been synthesized by treating aqueous solutions of the salt‐like cluster compounds K4Re4Q4(CN)12·nH2O with solutions of copper(II) chloride in aqueous ammonia containing diethylenetriamine. All six compounds have been characterized by single‐crystal X‐ray diffraction analysis. Compound 1has a chain‐like polymeric structure; orthorhombic, space group Pmn21. Compound 2has a molecular structure; triclinic, space group P$\bar 1$. Compounds 3and 4are isostructural and also exhibit molecular structures; monoclinic, space group P21/n. Compounds 5 and 6 are isostructural and display a cross‐bridged chain‐like polymeric structure; triclinic, space group P$\bar 1$. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003)