Using the alternating-current electrochemical technique, a novel pi-complex [Cu-2(Alobtr)(2)(H2O)(2)] (CH3C6H4SO3)(2) (1) was obtained starting from copper(II) p-toluenesulfonate and the 1-allyloxybenzotriazole (Alobtr) ethanol solution. The structure 1 should be considered as the first known example of Cu-I(p-CH3C6H4SO3) pi-coordination compound. Alobtr molecule acts as a chelate pi, sigma-ligand (being attached to the Cu(I) by means of allylic C=C bond and the two triazole N atoms) and forms centrosymmetric [Cu-2(Alobtr)(2)(H2O)(2)](2+) dimers. Cationic fragments and pTsO anions are connected by means of (Ow)H center dot center dot center dot O hydrogen bonds into 1D chains. Laser stimulated third harmonic generation for fundamental wavelength 1540 nm is explored. (C) 2018 Elsevier B.V. All rights reserved.