%0 Journal Article %A Bilyk, Alexander %A Hall, Annegret K. %A Harrowfield, Jack M. %A Hosseini, M. Wais %A Skelton, Brian W. %A White, Allan H. %D 2001 %T Systematic Structural Coordination Chemistry of p-tert-Butyltetrathiacalix[4]arene:  1. Group 1 Elements and Congeners %U https://acs.figshare.com/articles/journal_contribution/Systematic_Structural_Coordination_Chemistry_of_i_p_i_-_i_tert_i_-Butyltetrathiacalix_4_arene_1_Group_1_Elements_and_Congeners/3601098 %R 10.1021/ic001008c.s002 %2 https://ndownloader.figshare.com/files/5689059 %K proton coordination %K unsolvated forms %K calixarene moieties %K Cs complexes %K tert %K thiacalixarene monoanion %K Cs ions %K macrocyclic ring %K polyhapto Cs %K Congeners Determinations %K butyltetrathiacalix %K Rb ions %K Na %K Systematic Structural Coordination Chemistry %K alkali metal derivatives %K form part %K Li %K crystal structures %K alkali metal ions %K sulfur atoms %X 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 p-tert-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 p-tert-butylcalix[4]arene, there is no similarity in the structures of the Cs complexes, with the present structure showing no evidence of polyhapto Cs+−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+ complex, where two K+ 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”, p-tert-butyltetrathiacalix[4]arene ligand itself. %I ACS Publications