Françoise Arnaud-Neu, Geraldine Barrett, Denis Corry, Suzanne Cremin, George Ferguson, John F. Gallagher, Stephen J. Harris, M. Anthony McKervey and Marie‐Jose Schwing‐Weill
The effect of chemical modification of the lower rim of
p-tert-butylcalix[4]-, [5]- and [6]-arenes has
been analysed with respect to cation binding by thioamide
podands. Extraction data for metal picrates from water into
dichloromethane are discussed. CuII, PbII
and AgI ions are extracted efficiently by all the
thioamides studied, whereas extraction of CdII only
reaches significant levels with the pentamer derivative. Unlike
their calixarene amide counterparts, these thioamides have no
affinity in extraction for either alkali or alkaline earth
metals. The X-ray molecular structure of a
thioamide–PbII(ClO4)2 complex
and, for comparison, that of an
amide–CuII(ClO4
)2
complex have been determined. Both complexes exist in the cone
conformation with the metal ion encapsulated by the heteroatoms
on the lower rin. The crystal structure of the lead complex
derivative
5·Pb(ClO4
)2·EtOH·0.5
H2O, was solved by Patterson methods and
refined by block diagonal least-squares analysis. The crystals
are triclinic, space group P
,
a = 13.394(6),
b = 13.459(6),
c = 26.711(4) Å,
a = 78.33(2),
β = 87.62(2),
γ = 60.46(2)° with
R = 0.108 for 4417 observed reflections.
The Pb2+ is bonded to the four ethereal oxygen and
four thiocarbonyl sulfur atoms, [Pb–O, 2.65(2) to 2.72(2),
mean value 2.68(3) Å; Pb–S, 2.82(1) to 2.95(1) with
a mean of 2.91(3) Å]. The crystal structure of the copper
calixarene complex
2·Cu(ClO4
)2·H2O
·1.4CH3OH·EtOH, was solved by
direct methods and refined by block-diagonal least-squares
methods. The crystals are tetragonal, space group
P4/ncc a = 17.147(2),
c = 28.054(4) Å, with
R = 0.079 for 1482 observed reflections.
The Cu2+ resides on a four-fold axis and is bonded to
the four carbonyl oxygen atoms [Cu–O, 1.926(6) Å].
Four ethereal oxygen atoms are at a distance of 2.963(6) Å
from the metal ion.