One-, two- and three-dimensional copper(I) and silver(I) complexes of 2,11-dithia[3.3]paracyclophane

Abstract

Two copper(I) and one silver(I) complex of 2,11-dithia[3.3]paracyclophane (dtpcp), [Cu₂Br₂(dtpcp)(MeCN)₂]1, [Cu₂I₂(dtpcp)₂]·thf 2 and [Ag(dtpcp)(NO₃)]3, have been synthesized and their molecular structures determined by X-ray crystallography. All three structures contain an infinite network comprising metal cations linked via ditha-bridged paracyclophane and the counter anions. Complexes 1 and 2 are not isostructural. The repeating dinuclear units [Cu₂Br₂(dtpcp)(MeCN)₂] joined by dtpcp in 1 generate a one-dimensional polymeric chain running parallel to a diagonal axis of the triclinic cell. Complex 2 is a two-dimensional sheet structure in which a large ring containing six copper atoms includes a tetrahydrofuran molecule as guest inside the open cavity. The one-nitrate oxygen bridging two metal centres in complex 3 yields a unique three-dimensional channel framework of silver(I) ions. The iodine-doped black products of compounds 1–3 at room temperature exhibited conductivities of 10^–5.9, 10^–5.1 and 10^–4.7 S cm^–1, respectively.