Electrocrystallisation and single crystal structure determination of Bis(2,2′-bipyridyl)silver(II) perchlorate [Ag(bipy)2](ClO4)2

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 (P1¯; a=7.949(2)Å, b=10.236(2)Å, c=14.639(3)Å, α=78.57(3)°, β=81.63(3)°, γ=79.60(3)°, R1=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°. The axially oriented perchlorate counter anions are weakly coordinated, as indicated by Ag–O distances found to be larger than 3.2Å. The molecular complex can be described as an isolated, distorted octahedral unit [4+2] with an O–Ag–O angle of 158.5°. 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 1.71μB, at 300K which is close to the spin only value for a d9-system.