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Abstract:
Here we describe the electrocrystallization of [Ag(bpy)(2)](ClO4)(2) (bPy = 2,2'-bipyridine) its crystal structure and magnetic properties. Electrocrystallisation of the divalent silver complex [Ag(bpy)(2)](ClO4)(2) proceeds via formation and electrooxidation of the [Ag(bpy)(2)](+) intermediate. The single crystal structure analysis (P (1) over bar; a = 7.949(2) angstrom, b = 10.236(2) angstrom, c = 14.639(3) angstrom, alpha = 78.57(3)degrees, beta = 81.63(3)degrees, gamma = 79.60(3)degrees, R-1 = 0.0462) reveals that silver(II) is coordinated by two bipyridine ligands in a distorted square-planar manner displaying a dihedral angle ((bpy)-Ag-(bpy)) of 27.3 degrees. The axially oriented perchlorate counter anions are weakly coordinated, as indicated by Ag-O distances found to be larger than 3.2 angstrom. The molecular complex can be described as an isolated, distorted octahedral unit [4+2] with an O-Ag-O angle of 158.5 degrees. Thus the title compound is distinct from one-dimensional chain like structures of related copper(II) compounds or previously reported [Ag(bpy)(2)(NO3)](NO3). Magnetic measurements suggest that [Ag(bpy)(2)](ClO4)(2) behaves according to the Curie law. The effective magnetic moment is found to be 1.71 mu(B), at 300 K which is close to the spin only value for a d(9)-system. (C) 2012 Elsevier Ltd. All rights reserved.
