Systematic Structural Coordination Chemistry of <i>p</i>-<i>tert</i>-Butyltetrathiacalix[4]arene:  1. Group 1 Elements and Congeners Alexander Bilyk Annegret K. Hall Jack M. Harrowfield M. Wais Hosseini Brian W. Skelton Allan H. White 10.1021/ic001008c.s001 https://acs.figshare.com/articles/dataset/Systematic_Structural_Coordination_Chemistry_of_i_p_i_-_i_tert_i_-Butyltetrathiacalix_4_arene_1_Group_1_Elements_and_Congeners/3601095 Determinations of the crystal structures of complexes of the alkali metal ions with, in the case of Li, the dianion and, in the cases Na−Cs, the monoanion of <i>p</i>-<i>tert</i>-butyltetrathiacalix[4]arene have shown that both the sulfur atoms which form part of the macrocyclic ring, as well as the pendent phenolic/phenoxide oxygen donor atoms, are involved in coordination to these metals. Although the Li and Na complex structures are similar to those of the corresponding complexes of <i>p</i>-<i>tert</i>-butylcalix[4]arene, there is no similarity in the structures of the Cs complexes, with the present structure showing no evidence of polyhapto Cs<sup>+</sup>−π interactions. Instead, the complex crystallizes as a ligand-bridged (S-, O-donor) aggregate of three Cs ions, solvent molecules, and four calixarenes, somewhat like the Rb complex, though here four Rb ions are present, and higher in aggregation than the K<sup>+</sup> complex, where two K<sup>+</sup> ions are sandwiched between two calixarene moieties. The triethylammonium complex of the thiacalixarene monoanion, though formally analogous in that it involves a monocation, has a simpler structure than any of the alkali metal derivatives, based formally on proton coordination (H-bonding). However, interestingly, it can be isolated in both solvated (dmf, dmso) and unsolvated forms, as indeed can the “free”, <i>p</i>-<i>tert</i>-butyltetrathiacalix[4]arene ligand itself. 2001-01-13 00:00:00 proton coordination unsolvated forms calixarene moieties Cs complexes tert thiacalixarene monoanion Cs ions macrocyclic ring polyhapto Cs Congeners Determinations butyltetrathiacalix Rb ions Na Systematic Structural Coordination Chemistry alkali metal derivatives form part Li crystal structures alkali metal ions sulfur atoms