SERENDIPITOUS SYNTHESIS OF A Cu(OAc)2 COMPLEX VIA CuCl2 CATALYZED OXIDATION OF 2-BUTANONE: SYNTHESIS, CRYSTAL STRUCTURE, AND MAGNETIC BEHAVIOR OF (5-NAP)2(CH3COO)4Cu2∙nH2O (n = 0 AND 2) (5-NAP=2-AMINO-5-NITROPYRIDINE)

A copper (II) catalyzed Baeyer-Villiger reaction of 2-butanone in the presence of oxygen and 2-amino-5-nitropyridine produced crystals of (bis-2-amino-5-nitropyridine)tetraacetatedicopper(II) dehydrate, (1). 1 and its anhydrous form, (bis-2-amino-5-nitropyridine)tetraacetatedicopper(II), (2), were then synthesized directly from Cu(CH3COO)2∙H2O and 2-amino-5-nitropyridine. Crystals of both compounds were grown using slow evaporation, and characterized using IR, combustion analysis, X-ray powder diffraction, single crystal X-ray diffraction, and temperature-dependent magnetic susceptibility measurements. 1 and 2 are both monoclinic and crystallize in the space groups P21/c and C2/m, respectively. 2 exhibits 2-fold disorder in the 2-amino-5-nitropyridine molecule that arises due to symmetry. Both compounds pack in sheets of isolated dimers, and exhibit strong antiferromagnetic interactions within the dimers (J = -442(5) and -471(5) K for 1 and 2 respectively).
European Chemical Bulletin, Vol 4, No 1-3 (2015): European Chemical Bulletin