Syntheses And Crystal Structures Of P-sulfonatocalix[6]arene Complexes

Calixarenes have been the third important family in the field of supramolecular chemistry like crown ethers and cyclodextrins because of their synthetic availability, ease of modification in lower and upper rim,and the presence of cavities capable of binding a variety of species. wherein sulfonated calix[n]arenes (n= 4,5,6,8) are attracting significant attention due to highly Water solublility and less toxicity. Among them, p-Sulfonatocalix[4]arene has been the most widely studied , mainly due to its ability to retain a steady cone conformation. In contrast to p-sulfonatocalix[4]arene , p-sulfonatocalix[6]arene (C6AS) is a more highly charged and conformationally flexible molecule, a fact which renders solid-state complex formation and structural characterization a more formidable challenge. This is reflected in the small number of solid-state supramolecular structures that incorporate C6AS.On the basis of the study of complexes of p-sulfonatocalix[4]arene, In this paper, we design to synthesize two supramelocular complexes. One is p-sulfonatocalix[6]arene with silver ion and ethylenediamine, the other is p-sulfonatocalix[6]arene with copper ion and 1,10-phenanthroline. The experimental results as following:1. At first, we get p-sulfonatocalix[6]arene by the reaction of calix[6]arene and H2SO4(98%),Then treating the mixture with ethyl ether .This method has not been found in reports today.All the compounds were characterized by 1H NMR and IR spectrum. The result was the same as that in the references. They are the target host molecular.2.complex (4) Ag₁₃[C₂H₈N₂]₁₄[C₄₂H₃₀S₆O₂₄]₂NaCl₂[H₂O]₂₃ was obtained by p-sulfonato calix[6]arene and Ag+,using ethylenediamine to adjust pH=12 by slowly evaporation at room temperature. Unit cell dimensions: a=21.625(5)(A|°), b=22.695(5)(A|°), c=34.756(5)(A|°), ?=90.000(5) (A|°),α=97.159(5)(A|°),β=90.000(5)(A|°), V = 16925(6)(A|°)³,Single-crystal structure has indicated that there are two p-sulfonatocalix[6]arene molecules in an common"up-down"double cone conformation,Ag⁺ ions and ethylenediamine formed a long chain in which AG12 atom were combined to O44 of p-sulfonatocalix[6]arene in the solid states of complex(4).3.The supramolecular complex (5) [Cu(C₁₂H₈N₂)]₈[C₄₂H₃₀S₆O₂₄]₂Cl₄[H₂O]₆₀ has been synthesized by slowly evaporating the aqueous solutions of CuCl₂/1,10-phenanthroline and p-sulfonatocalix[6]arene at room temperature in acid solution. Unit cell dimensions: a=20.0880(5)(A|°), b=21.5630(5)(A|°), c=27.0270(5)(A|°),α=105.882(5)(A|°),β=95.472(5)(A|°),γ=95.064(5) (A|°), V = 11128.50(2)(A|°)³. In the structure, the C6AS molecule acts as a quadridentate ligand and is connected with four copper ions. The extended structure is constructed by the stacking of these polymer viaÏ€-Ï€stacking. Some isolated [Cu(phen)(H₂O)₄]²⁺ cations and solvent molecules are located in the interstices.