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

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 CuCl2·2H2O, NaSCN, and dpa afforded the copper (I) thiocyanate coordination polymer [Cu2(SCN)2(dpa)] (2), whose single crystal structure revealed unprecedented 1-D [Cu2(SCN)2] zig-zag staircase motifs constructed via connection of the Cu2S2 “stair steps” at their adjacent sides via μ3-1,1,3-SCN anions. The 3-D structure of 2 is propagated by covalent linkage of each [Cu2(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.