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

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 3 ‐dimethyldithiocarbamato)dodeca‐μ 3 ‐iodido‐hexa‐μ 2 ‐iodido‐tetracopper(I)copper(II)hexalead(II)]], {(C 16 H 36 N) 2 [Cu 4 I Cu II Pb 6 (C 3 H 6 NS 2 ) 2 I 18 ]} n , (I), and poly[[μ 3 ‐iodido‐tri‐μ 2 ‐iodido‐iodido[bis(1,10‐phenanthroline)copper(I)]copper(I)copper(II)lead(II)] hemiiodine], {[Cu I Cu II PbI 5 (C 12 H 8 N 2 ) 2 ]·0.5I 2 } n , (II), under solution and solvothermal conditions, respectively. Compound (I) contains two‐dimensional anionic layers, which are built upon the linkages of Cu II (S 2 CNMe 2 ) 2 units and one‐dimensional anionic Pb/I/Cu I 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 5 ] square pyramids, [Cu I I 4 ] tetrahedra and [Cu II N 4 I] 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 2 molecules lie in the voids of the structure.