Novel anionic dicyanamidocuprate(II) structural motifs through cation templation

The crystal structures and magnetic properties of two new salts containing polymeric dicyanamidocuprate(II) anions are reported. Subtle changes in cation templation effects, crystallization conditions, and the coordination geometry of the metal center result in dramatic changes in the structure of the anionic framework. We report that the (PPh4)Cu(dca)3H2O [dca = dicyanamide, N(CN)2-] salt contains singly bridged μ1,5-dca chains that are linked into a two-dimensional network through coordinated water molecules. Replacement of one of the cation phenyl groups with a butyl group results in the formation of the (PPh3Bu)2Cu(dca)4 salt, which contains doubly bridged μ1,5-dca chains. Only negligibly weak magnetic interactions were observed in both compounds.

Two new anionic dicyanamidocuprate(II) coordination polymers, (PPh4)Cu(dca)3H2O and (PPh3Bu)2Cu(dca)4, have been crystallized. The singly bridged μ1,5-dicyanamide chains in the former are linked into a two-dimensional array through hydrogen bonding, while in the latter, doubly bridged μ1,5-dicyanamide chains are formed. Long range magnetic order has not been observed in either compound.Figure optionsDownload as PowerPoint slide