Divalent Nickel and Monovalent Copper Pseudohalide Coordination Polymers Incorporating the Kinked Organodiimine 4,4′‐Dipyridylamine: From a (4,4)‐Type Lamellar Motif to an Unprecedented Staircase Morphology

Abstract

Abstract The divalent nickel isothiocyanate coordination polymer [Ni(NCS) 2 (dpa) 2 ] ( 1 ) has been prepared in high yield via the hydrothermal combination of Ni(SCN) 2 with the kinked tethering ligand 4,4′‐dipyridylamine (dpa), and characterized via single crystal X‐ray diffraction, infrared spectroscopy and elemental and thermal analysis. 1 manifests offset stacked 2‐D (4,4)‐topology layered motifs organized into 3‐D via interlamellar supramolecular N–H···S hydrogen bonding. Hydrothermal reaction of CuCl 2 ·2H 2 O, NaSCN, and dpa afforded the copper (I) thiocyanate coordination polymer [Cu 2 (SCN) 2 (dpa)] ( 2 ), whose single crystal structure revealed unprecedented 1‐D [Cu 2 (SCN) 2 ] zig‐zag staircase motifs constructed via connection of the Cu 2 S 2 “stair steps” at their adjacent sides via μ 3 ‐1,1,3‐SCN anions. The 3‐D structure of 2 is propagated by covalent linkage of each [Cu 2 (SCN) 2 ] staircase to four others through dipodal dpa tethering ligands, enhanced by N–H···S and C–H···S supramolecular interactions to two other staircases.