Synthesis and Characterization of an Unusual High Coordination Number Alkylmercury Complex with Topologically Linear Ligand

摘要

The organomercurial complex [Hg(CH2COCH3)(L)(OCLO3)] where L is topologically linear 2,6-bis([(2-pyridinylmethyl)oxy]methyl)pyridine has been isolated and characterized by X-ray crystallography. The new compound crystallizes in the monoclinic space group P2(1)/c with unit cell parameters: a = 8.1680(3) , b = 16.5794(5) , c = 17.3957(5) , beta = 101.2944(13)A degrees, V = 2310.11(13) (3), Z = 4. The mercury atom has short bonds to the acetonyl methylene carbon (2.101(3) ) and one terminal pyridyl nitrogen of L (2.161(2) ) with C-Hg-N angle of 170.67(10)A degrees. A distended N2O3 pentagonal girdle involving the remaining four L donor atoms and one perchlorate oxygen complete a distorted pentagonal bipyramidal coordination geometry around mercury. The supramolecular solid state architecture is sustained by intermolecular interactions between pyridyl rings. The yielded product was confirmed by ESI-MS and H-1 NMR. In solution, the acetonyl methylene protons have Delta delta 0.013 ppm indicating hindered rotation around the methylene carbon-carbonyl carbon bond. In contrast, the solid state chirality of the multidentate ligand was lost in solution.