Synthesis and Structure of [Cu(Hapn)]NO3]NO3, [Cu(Hapn)(H2O)2]SiF6, [Cu(Hapn)(H2O)BF4]BF4∙H2O and [Cu(Hapn)(NH2SO3)2] π-complexes (apn = 3-(prop-2-en-1-ylamino)propanenitrile)

Abstract

Four copper(I) π-complexes: [Cu(Hapn)NO₃]NO₃ (1), [Cu(Hapn)(H₂O)₂]SiF₆ (2), [Cu(Hapn)(H₂O)BF₄]BF₄·H₂O (3) and [Cu(Hapn)(NH₂SO₃)₂] (4) were prepared using alternating-current electrochemical technique, starting from alcohol solutions of 3-(prop-2-en-1-ylamino)propanenitrile (apn) titrated with appropriate acid and copper(II) salts (Cu(NO₃)₂∙3H₂O, CuSiF₆∙4H₂O, Cu(BF₄)₂∙6H₂O or Cu(NH₂SO₃)₂∙xH₂O, respectively). Obtained compounds were characterized by single-crystal X-ray diffraction and partially by IR spectroscopy. In the structures of complexes 1, 2 and 4 Cu(I) cation possesses a tetrahedral environment formed by the C=C bond of one organic cation Hapn, the N atom of ciano group from another Hapnmoiety, and two O atoms (from NO₃^– anions in 1, from H₂O molecules in 2) or N atoms (NH₂SO₃^– anions in 4). In compound 3 strongly pronounced trigonal-pyramidal coordination environment of Cu(I) is formed by a mid-point of C=C-bond of one Hapncation, nitrogen atom (of cyano group) of another Hapn unit, O atom of H₂O molecule in the basal plane, and F atom of BF₄^– anion at the apical position.