Hydrophilic interior between hydrophobic regions in inverse bilayer structures of cation-11'-binaphthalene-2,2'-diyl phosphate saltst

摘要

A series of 1,1'-binaphthalene-2,2'-diyl phosphate (BNPPA~-)salts have been synthesized.Their crystal packings show a separation of the hydrophobic naphthyl and hydrophilic (RO)_2PO_2~-phosphate/cation/solvate regions.Hydrogen bonding in the latter is the driving force for "inverse bilayer" formation,with a hydrophilic interior exposing the hydrophobic binaphthyl groups to the exterior.Stacking of the inverse bilayers occurs less through pi-pi and more through CH...pi interactions between the naphthyl groups,which correlates with the formation of thin crystal plates along the stacking direction.Cations used with R-or rac-BNPPA~- are protonated isonicotin-1-ium amide (1),isonicotin-1-ium acid (2),guanidinium (3),the metal complexes trans-tetraammine-dimethanol-copper(II)(4),trans-diaqua-tetramethanol-copper(II)(5)and cisdiaqua-bis(ethylene diamine)-nickel(II)(6).Crystallization occurs with inclusion of water and methanol solvent molecules,except in 2.Starting from R-BNPPA,inversion takes place with calcium acetate to give 1 as the racemate.2 is crystallized as the .R-BNPPA salt.The inversion-symmetrical complex trans-[Cu(H_2O)_2(CH_3OH)_4]~(2+)in 5 has Cu-OH_2 bond lengths of 1.937(4)A,and Cu-O(methanol)of 2.112(4)and 2.167(4)A,corresponding to a compressed tetragonal geometry.