Bilayers, Corrugated Bilayers, and Coordination Polymers of <i>p</i>-Sulfonatocalix[6]arene

Exploration into the host−guest supramolecular chemistry of p-sulfonatocalix[6]arene with pyridine N-oxide and 4,4‘-dipyridine N,N‘-dioxide has resulted in the characterization of three new structural motifs with the calixarene in the “up−down” double partial cone conformation. Two are hydrogen-bonded network structures formed with pyridine N-oxide and either nickel or lanthanide metal counterions (1 and 2, respectively). Complex 1 displays host−guest interactions between pyridine N-oxide and the calixarene in the presence of hexaaquanickel(II) counterions. Complex 2 demonstrates selective coordination modes for different lanthanides involving the calixarene and pyridine N-oxide. The third structure, 3, is a coordination polymer which is formed with 4,4‘-dipyridine N,N‘-dioxide molecules which span a hydrophilic layer and join lanthanide/p-sulfonatocalix[6]arene fragments. Although complexes 1−3 all have the calixarene in the “up−down” double partial cone conformation, 1 and 3 form bilayer arrangements within the extended structures while 2 forms a previously unseen corrugated bilayer arrangement.