Hydrogen-Bonded Helical Array, Sodium-Ion-Mediated Head-to-Tail Chain, and Regular Ionic Bilayer: Structural Diversities of p-Sulfonatothiacalix[4]arene Tetranuclear Cluster Units

摘要

Exploration into the supramolecular chemistry of p-sulfonatothiacalix[4]arene (TCAS) tetranuclear clusters with methylviologen dihexafluorophosphate (MV(PF6)(2)) and 4,4'-diaminodiphenyl ether (4,4'-Dadpe) has resulted in three interesting structural motifs: {[MV][Co-4(TCAS)(mu(4)-SO4)(H2O)(8)]center dot 8H(2)O}(n) (1), {[Na(H2O)(2)][Co-4(TCAS)(mu(5)-SO4)(H2O)(7)(4,4'-HDadpe)]center dot 6H(2)O), (2), and {[MV][CU4(TCAS)(mu(4)-SO4)(H2O)(4)]center dot 9H(2)O}(n) (3). In complex 1, the assembly of TCAS tetracobalt(II) clusters driven by multiple hydrogen bonding forms supramolecular helices along three crystallographic axes, while TCAS tetracobalt(II) clusters in complex 2 have assembled into a rare head-to-tail chain mediated by sodium ions in the presence of 4,4'-Dadpe. Complex 3 features a regular ionic bilayer structure, in which TCAS tetracopper(II) clusters and MV2+ cations form negative and positive layers, respectively.