2D Honeycomb Coordination Polymers from 2,2′-Dithiobis(pyridine N -oxide) and Bismuth(III) Halides

Two bismuth(III) coordination polymers, namely [Bi 2 X 6 ( µ -dtpo) 3 ] n [ X = Cl ( 1) , Br ( 2 ); dtpo = 2,2′-dithiobis(pyridine N -oxide)], were prepared using a crystal engineering strategy and structurally characterized by X-ray crystallography. In the isostructural compounds 1 and 2 (trigonal system, space group P -3 c 1), fac -configured Bi X 3 units as nodes are joined by the C 2 -symmetrical dtpo bridging ligand as spacers to generate 2D honeycomb layers with (6,3) topology. The 2D sheets stack along the [001] direction, resulting in virtually hexagonal channels parallel to this direction, which are occupied by disordered methanol and water molecules. The potential solvent area per unit cell volume is 42.2% for 1 and 44.0% for 2 . Graphical Abstract Two isostructural 2D honeycomb bismuth(III) coordination, synthesized from 2,2′-dithiobis(pyridine N -oxide) and bismuth(III) halides are described.