In the solid state, the macrocyclic polyether, tetrabenzo[24]crown-8 (TB24C
8), is an interesting molecule. When crystallized from MeCN solution, a bis
-MeCN clathrate is formed, in which the TB24C8 macroring-by adopting a conf
ormation with approximate tennis-ball-seam symmetry (D-2d)-forms C-H...pi-l
inked supramolecular chains. However, when crystallized from CHCl3/Et2O sol
ution, the TB24C8 crystallizes alone-adopting a self-filling 'flattened-out
' conformation with Ci symmetry-forming C-H...pi-linked sheets which stack
upon one another by virtue of-yet again (!)-C-H...pi hydrogen bonds. By con
trast, the solid-state superstructure of the [2]pseudorotaxane formed betwe
en TB24C8 and dibenzylammonium hexafluorophosphate (DBA-PF6), contains no C
-H...pi interactions. However, a multitude of more enthalpically favorable
C-H...F hydrogen bonds-to a highly-ordered matrix of PF6- anions-stabilizes
the formation of the [2]pseudorotaxane array. (C) 2000 Elsevier Science Lt
d. All rights reserved.