Honeycombs, herringbones and brick-walls; three-fold guest-dependent variation in copper trimesate complexes bearing sulfimideligands

Abstract

Reaction of a solution of CuSO₄ and S,S′-diphenylsulfimide, Ph₂SNH 1, with sodium salts of trimesic acid (H₃tma) in MeOH gives the 2-D coordination network [Cu₃(Ph₂SNH)₆(tma)₂] in which each trimesate is bound to three copper centres. Addition of other solvents to the reaction mixture causes a change in the shape of the network. By this route, three forms have been prepared and characterised by X-ray crystallography. These include the known honeycomb, 2, and brick-wall, 3, motifs and a herringbone, 4, arrangement which is novel for transition metal-containing trimesate complexes. Key to the supramolecular isomerism observed is the ability of 1 to facilitate structural isomerism at copper(II) centres. In contrast to 2 in which the copper centres are square planar, 4 is analogous to an inter-allogon, with both planar and tetrahedral copper centres. Also prepared is a related complex 5 which is composed of discrete units of three copper centres. These are further linked into a 2-D network by hydrogen bonds.