A thiocyanato-bridged layer structure composed of symmetrical, dithiocyanato(N,S)-bridged dimers of heterotrinuclear alkoxo-bridged Cu₂Pb units; synthesis from zerovalent copper, structural, spectroscopic and magnetic studies

Abstract

A novel mixed-metal compound [{Cu₂Pb(SCN)₃L₃}₂] has been prepared from zerovalent copper and lead thiocyanate in an acetonitrile solution of 2-dimethylaminoethanol (HL). The compound, which crystallizes in the monoclinic space group P 2₁/c with a = 14.5786(1), b = 17.4145(2), c = 10.5194(1) Å, β = 105.11(1)° and Z = 4, has been characterized by a range of spectroscopic methods. The crystal structure contains symmetrical dimers of heterotrinuclear alkoxo-bridged Cu₂Pb units in which dimerization has occurred through bridging of NCS via the axial positions on the copper ions. The so-formed hexanuclear units are linked by Pb  · · ·  S interactions between adjacent units to form layered supramolecular assemblies along the b axis of the crystal. The magnetic behaviour can be understood on the basis of the structure, and corresponds to that of a weakly antiferromagnetically coupled dinuclear unit. The small value of the antiferromagnetic coupling can be explained by the roof-shaped CuO₂Cu unit, which prevents the magnetic orbitals from undergoing significant overlap.

References

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