Systematic Structural Coordination Chemistry of p-tert-Butyltetrathiacalix[4]arene: Main Group Metal Complexes Other Than Those of Group 1

In extension of previous work involving structural characterisation of complex salts formed between main group 1 metal ions and p-tert-butyltetrathiacalixarene, LH4, the present study encompasses complexes with a wider array of main group 2, 13, 14 metal ions. For group 2, single-crystal X-ray structural characterisation of Ca(LH3)(2)center dot 3dmf (1a), {Ca(LH2)center dot 3dmf}2 (1b), Ba(LH3)(2)center dot 6dmf (2a) and BaCO3 center dot 3Ba(LH3)(2)center dot 3H(2)O center dot 3CH(3)CN center dot 12.25CH(2)Cl(2) (2b) provides models for variouscoordination units. For group 13, this applies to {Ga(OH)-(LH2)center dot 3.5dmf}(2) (3), {In(LH)center dot 4EtOH center dot 2CH(2)Cl(2)}(2) (4a) and {In(OH)(LH2)center dot 3CH(2)Cl(2)}(4) (4b), and for group 14, to OPb4(LH)(2)center dot 6dmf center dot dmso center dot 2H(2)O (5). Overall, these define mononuclear (la, 2a), binuclear (1b, 3, 4b) and tetranuclear (2b, 4b, 5) species. The calixarene cavities frequently include solvent molecules, though this capacity is clearly influenced by the nature of the bound metal ion(s) and their binding, as well as the associated impact on the conformation of the calixarene ligand(s).