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.