Stability constants and enthalpy changes determined by calorimetric ti
trations and supported by selected NMR titrations are reported for the
complexation of sodium and potassium cations with 18 different crown
ethers containing nitrogen atoms with different number, location and s
ubstitution pattern. The data, measured in methanol mostly with potass
ium salts, are compared to literature data; they show striking differe
nces between all-oxygen analogs and the macrocycles with NH groups. In
contrast, affinities with aza crown ethers bearing alkyl groups at th
e nitrogen as well as with the cryptand [2.2.2] come closer to the com
plexation free energies predicted from the number and electron donatin
g capacity of the ligand heteroatoms. This is rationalised on the basi
s of molecular mechanics calculations, showing that a NH-containing cr
own predominates in conformations with axial N lone pairs, due to thei
r repulsive electrostatic interactions with the ring oxygen atoms. Rep
lacement of the hydrogen by alkyl groups forces the lone pairs to an e
quatorial position, thus enabling better complex formation, as borne o
ut by experiment. In Line with these arguments the IgK differences are
with some exceptions more due to Delta H than to T Delta S difference
s. The calorimetric data show linear isoequilibrium correlations betwe
en T Delta S and Delta H, with slopes between those observed with othe
r crown ether and cryptand complexes. Preliminary investigations of so
me synthetic macrocyclic amide precursors yield appreciable complexati
on only, if the two carbonyl oxygens can come in close contact with th
e guest cation. Computer aided molecular modelling shows that this is
possible in a small 15C5-derivative, in which the polyethylenglycol cy
cle only serves as ring template without binding contributions from th
e ether oxygen atoms.