Cation‐Dependent Nuclearity of New HomolepticAzidocuprates(II), From Discrete Ions toAnionic Strands and Sheets

In chemical reactions of copper(II) acetate dihydrate with imidazolium azide salts in ethanol solution several new homoleptic azidocuprates(II) were obtained. In dependency of the used counter cation various different azidocuprate moieties were crystalized. The doubly charged DMMDIm2+ cation facilitates the formation of mononuclear [Cu(N3)4]2– complex anions, while the utilisation of the (PeMIm)+ ion enables the isolation of a di‐nuclear [Cu2(N3)6]2– salt. By using the unsymmetrical imidazolium ions (BMIm)+ or (EMIm)+ salts with the tri‐nuclear [Cu3(N3)8]2– complex anion are obtained. With the (DML)+ cation an azidocuprate(II) crystallizes , which contains both [Cu(N3)4]2– and the [Cu2(N3)6]2– anion. The anions in the salt with the (PeMIm)+ cation are interconnected through further Cu−N bonds and form layers with a 2D‐honecomb structure. The tri‐nuclear units in the (BMIm)+ and the (EMIm)+salts form coordination strands of different structures.