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(μ3-dimethyldithiocarbamato)dodeca-μ3-iodido-hexa-μ2-iodido-tetracopper(I)copper(II)hexalead(II)]], {(C16H36N)2[Cu4 ICuIIPb6(C3H6NS2)2I18]} n , (I), and poly[[μ3-iodido-tri-μ2-iodido-iodido[bis(1,10-phenanthroline)copper(I)]copper(I)copper(II)lead(II)] hemiiodine], {[CuICuIIPbI5(C12H8N2)2]·0.5I2} n , (II), under solution and solvothermal conditions, respectively. Compound (I) contains two-dimensional anionic layers, which are built upon the linkages of CuII(S2CNMe2)2 units and one-dimensional anionic Pb/I/CuI 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 [PbI5] square pyramids, [CuII4] tetrahedra and [CuIIN4I] 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. I2 molecules lie in the voids of the structure.