Syntheses and crystal structures of two heterometallic iodoplumbates containing mixed-valence copper(I/II)

Abstract

Mixed-valence copper(I/II) atoms have been introduced successfully into a Pb/I skeleton to obtain two heterometallic iodoplumbates, namely poly[bis(tetra-n-butylammonium) [bis(μ-dimethyldithiocarbamato)dodeca-μ-iodido-hexa-μ-iodido-tetracopper(I)copper(II)hexalead(II)]], {(CHN)[CuCuPb(CHNS)I]}, (I), and poly[[μ-iodido-tri-μ-iodido-iodido[bis(1,10-phenanthroline)copper(I)]copper(I)copper(II)lead(II)] hemiiodine], {[CuCuPbI(CHN)]·0.5I}, (II), under solution and solvothermal conditions, respectively. Compound (I) contains two-dimensional anionic layers, which are built upon the linkages of Cu(SCNMe) units and one-dimensional anionic Pb/I/Cu chains. Tetra-n-butylammonium cations are located between the anionic layers and connected to them via C-H...I hydrogen-bonding interactions. Compound (II) exhibits a one-dimensional neutral structure, which is composed of [PbI] square pyramids, [CuI] tetrahedra and [CuNI] trigonal bipyramids. Face-to-face aromatic π-π stacking interactions between adjacent 1,10-phenanthroline ligands stabilize the structure and assemble compound (II) into a three-dimensional supramolecular structure. I molecules lie in the voids of the structure.