Synthesis and Structure of Cu(Hapn)NO3NO3, Cu(Hapn)(H2O)2SiF6, Cu(Hapn)(H2O)BF4BF4∙H2O and Cu(Hapn)(NH2SO3)2 π-complexes (apn = 3-(prop-2-en-1-ylamino)propanenitrile)

摘要

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.