Synthesis, crystal structure and magnetic properties of a two-dimensional cyanide-based heterometallic coordination polymer with cationic piperazinium ligands: poly[aquatetra-μ2-cyanido-κ(8)C:N-dicyanido-κ(2)C-(piperazinium-κN(4))cobalt(III)copper(II)]

Acta Crystallogr C Struct Chem. 2016 Jan;72(Pt 1):21-7. doi: 10.1107/S2053229615021361. Epub 2015 Dec 9.

Abstract

Cyanide as a bridge can be used to construct homo- and heterometallic complexes with intriguing structures and interesting magnetic properties. These ligands can generate diverse structures, including clusters, one-dimensional chains, two-dimensional layers and three-dimensional frameworks. The title cyanide-bridged Cu(II)-Co(III) heterometallic compound, [Cu(II)Co(III)(CN)6(C4H11N2)(H2O)]n, has been synthesized and characterized by single-crystal X-ray diffraction analysis, magnetic measurement, thermal study, vibrational spectroscopy (FT-IR) and scanning electron microscopy/energy-dispersive X-ray spectroscopy (SEM-EDS). The crystal structure analysis revealed that it has a two-dimensional grid-like structure built up of [Cu(Hpip)(H2O)](3+) cations (Hpip is piperazinium) and [Co(CN)6](3-) anions that are linked through bridging cyanide ligands. The overall three-dimensional supramolecular network is expanded by a combination of interlayer O-H...N and N-H...O hydrogen bonds involving the coordinated water molecules and the N atoms of the nonbridging cyanide groups and monodentate cationic piperazinium ligands. A magnetic investigation shows that antiferromagnetic interactions exist in the title compound.

Keywords: TOPOS analysis; antiferromagnetic coupling; cobalt(III); copper(II); crystal structure; heterometallic; hexacyanidocobaltate; hydrogen bonding; piperazinium; two-dimensional coordination polymer.

Publication types

  • Research Support, Non-U.S. Gov't