Reactions of PhenCuX2 (X = OOCMe, O3SCF3) with 3,5-Dimethylpyrazole: Effect of the Anion Nature on the Composition and Structure of the Complexes

The reaction of aqueous copper(II) acetate with phenanthroline (Phen) gave the complex PhenCu(OOCMe)2 ∙ 2MeCN (I), which was converted to the single crystals of the monomer PhenCu(OOCMe)2 ∙ 1.5CH2Cl2 (II) upon recrystallization of dichloromethane. Recrystallization of I from wet benzene gave the single crystals of PhenCu(OOCMe)2(OH2) ∙ 0.5 C6H6 ∙ 0.5MeCN (III) containing a coordinated water molecule. The reaction of I with 3.5 dimethylpyrazole (HDmpz) (1 : 2) resulted in the synthesis of PhenCu(OOCMe)2HDmpz ∙ 0.5H2O ∙ 0.5CH2Cl2 (IV) in which the pyrazole molecule occupied the same coordination site as the water molecule in III. The reaction of I with trifluoromethanesulfonic acid yielded PhenCu(OH2)(NCMe)(Otf)2 (V), which was also prepared by the reaction of copper acetate with HOtf followed by the addition of 1 mole of Phen ∙ H2O. Monomer V reacted with 2 moles of HDmpz to be converted to PhenCu(HDmpz)2(Otf)2 (VI). Compounds I–VI were characterized by elemental analysis data, IR spectra, and X-ray diffraction (CCDC nos. 1948544 (I), 1948541 (II), 1987813 (III), 1948542 (IV), 1948540 (V), 1948543 (VI)). The geometry of complexes and the effect of solvent used for the reactions and crystallization on the molecular packing in the crystals were considered on the basis of X-ray diffraction data.