Journal of Lipid Research, Vol 38, 361-372, Copyright © 1997 by Lipid Research, Inc.
Molecular association of normal alkanoic acids with their thallium(I) salts: a new homologous series of fatty acid metal soaps
M Fernandez-Garcia, MV Garcia, MI Redondo, JA Cheda, M Fernandez-Garcia, EF Westrum Jr and F Fernandez-Martin
Departamento de Quimica Fisica I, Universidad Complutense, Madrid, Spain.
A new homologous series of thallium(I) hydrogen dialkanoates, fatty acid
thallium soaps, from the dipropane up to the ditetradecane is reported for
the first time. This association with 1:1 stoichiometry is the only one
exhibited by the thallium derivatives. They have been prepared by
solidification of molten mixtures with equimolar proportions of acid and
corresponding neutral salt, through crystallization from an anhydrous
ethanolic solution of the mixture has also been successful in getting pure
compounds with largest chain lengths. Vibrational spectroscopies clearly
characterize these crystalline compounds as very strong hydrogen bonding
systems. Assignations of active modes in proton and carbon nuclear magnetic
resonance spectrometry (NMR) (in ethanol) and infrared (IR) and Raman
spectra (in solid state) are reported. According to X-ray diffraction (XRD)
they have monomolecular lamellar structures with the acyl chains arranged
up and down to the cation/H-bond network in a methyl-to-methyl fashion, and
vertically oriented to the basal plane. The acyl chains present all-trans
conformation and alternating configuration (perpendicular orthorhombic
subcell), like the beta'-phases of other kinds of lipids. Lamellar
thickness is reported for the six room- temperature crystalline members.
The molecular compounds present polymorphism, one crystal/crystal
transition at temperatures close to the peritectical melting. Phase
transition thermodynamics are also given and discussed with respect to
their acid and salt parents. Their incongruent melting involves nearly 90%
of the total enthalpic increments of both constituents' melting processes,
making these compounds potential thermal energy storage materials.