New Cu(II) compounds with ligands synthesized through nucleophilic addition of pyrazoles to dicyanamide. Synthesis, crystal structures and spectroscopy

摘要

Three newly synthesized ligands, i.e. (pyrazolecarbimido)-cyanoamine (abbreviated as Hdcapz), (3-methylpyrazolecarbimido) cyanoamine (abbreviated as Hdcampz) and (3,5-dimethylpyrazolecarbimido) cyanoamine (abbreviated as Hdcadmpz) are presented in this study, including the X-ray crystal structures for two of them, as well as their coordination behaviour with respect to Cu(II). The structures of 4 Cu(II) compounds with dmpzdca, i.e. the mononuclear compounds [Cu(dcadmpz)_2(H_2O)] (3), [Cu(dcadmpz) _2] (4), the polynuclear compound [Cu_3(dcadmpz) _4(CH_3OH)_(0.6)-(H_2O) _(0.4)](ClO_4)_2(CH_3OH) _(1.25)(H_2O)_(0.2) (5) and the triangular-based bis-trinuclear compound [Cu_3-(Hdcadmpz)_3(NO _3)_3(CH_3OH)_2]_2· [Cu_3(Hdcadmpz)_3(NO_3)_3(CH _3CN)] (6) are also presented, together with their spectroscopic properties (ligand field, EPR and IR). The geometry around the Cu(II) ion for 3 and 4 is square pyramidal. The three crystallographic independent Cu(II) ions in compound 5 have a distorted square pyramidal geometry. The trinuclear compound 6 consists of three different crystallographically independent trinuclear units with a total of 9 different independent Cu(II) ions. The geometry for the Cu(II) ions vary from distorted square pyramidal to distorted octahedral.