A new ligand bearing a tetrazol heterocyclic core -N,N-dimethyl-4-[5-(allylsulfanyl)-1Htetrazol-1-yl]aniline (Dasta)was synthesized and used for preparation of copper(I) π-complex. Alternating current electrochemical method was used to obtain [Cu(Dasta)(DastaH)][BF4]2·3.5H2O in form of single crystals suitable for X-ray study. This coordination compound crystallizes in monoclinic crystal system, space group I2/a (a = 15.946 (5) Å, b = 13.341(5) Å, c = 36.669(8) Å, β = 100.87(3)°, V = 7661(4) Å

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... , Z = 8). The structure is formed by layers composed of [Cu(Dasta)(DastaH)] 2+ cations and a half of fluoroborate anions while the other half of the counterions connects the layers by means of intercalation. The resulting structure possesses pores which host disordered water molecules.