Abstract: | Crystals of the title π‐complex, Cu4Cl6(C8H11N2)2]n, were obtained by means of alternating‐current electrochemical synthesis. The structure consists of infinite copper–chlorine chains to which 1‐allyl‐3‐aminopyridinium moieties are attached via a η2 Cu—(C=C) interaction. The two independent Cu atoms have distinct coordination environments. One is three‐coordinate, surrounded by two chloro ligands and the olefinic bond, whereas the second copper center is surrounded by a tetrahedral arrangement of four Cl atoms. The lower basicity of 3‐aminopyridine as compared with 2‐ and 4‐aminopyridine lowers the capacity of the organic ligand for donating to N—H?Cl hydrogen bonds and results in the formation of a large inorganic fragment. |