Temperature-Driven Mixing-Demixing Behavior of Binary Mixtures of the Ionic Liquid Choline Bis(trifluoromethylsulfonyl)imide and Water

The ionic liquid (2-hydroxyethylammonium)trimethylammonium) bis(trifluoromethylsulfonyl)imide (choline bistriflimide) was obtained as a supercooled liquid at room temperature (melting point = 30 degrees C). Crystals of choline bistriflimide suitable for structure determination were grown from the melt in situ on the X-ray diffractometer. The choline cation adopts a folded conformation, whereas the bistriflimide anion exhibits a transoid conformation. The choline cation and the bistriflimide anion are held together by hydrogen bonds between the hydroxyl proton and a sulfonyl oxygen atom. This hydrogen bonding is of importance for the temperature-dependent solubility proper-ties of the ionic liquid. Choline bistriflimide is not miscible with water at room temperature, but forms one phase with water at temperatures above 72 degrees C (equals upper critical solution temperature). H-1 NMR studies show that the hydrogen bonds between the choline cation and the bistriflimide anion are substantially weakened above this temperature. The thermophysical properties of water-choline bistriflimide binary mixtures were furthermore studied by a photopyroelectric technique and by adiabatic scanning calorimetry (ASC). By photothermal analysis, besides highly accurate values for the thermal conductivity and effusivity of choline bistriflimide at 30 degrees C, the detailed temperature dependence of both the thermal conductivity and effusivity of the upper and lower part of a critical water-choline bistriflimide mixture in the neighborhood of the mixing-demixing phase transition could be determined with high resolution and accuracy. Together with high resolution ASC data for the heat capacity, experimental values were obtained for the critical exponents alpha and beta, and for the critical amplitude ratio G(+)/G(-). These three values were found to be consistent with theoretical expectations for a three dimensional Ising-type of critical behavior of binary liquid mixtures.

Pyrimidine and pyrazine as N-donor ligands in mercurous complexes: [Hg-2(Pym)]NO3)(2), [Hg-2(Pym)](ClO4)(2), and [Hg-2(Pyp)(2)](ClO4)(2)

Colourless single crystals of [Hg-2(Pym)](NO3)(2), [Hg-2(Pym)](ClO4)(2) and [Hg-2(Pyp)(2)](ClO4)(2) were obtained from aqueous solutions of the respective components Hg-2(NO3)(2).2H(2)O, Hg-2(ClO4)(2).6H(2)O, pyrimidine (Pym) and pyrazine (Pyp). The crystal structures were determined from single-crystal X-ray diffractometer data. [Hg-2(Pym)](NO3)(2): monoclinic, C2/c, Z = 8, a = 1607.4(2), b = 652.79(7), c = 2000.5(2) pm, beta = 103.42(2)degrees, R-all = 0.0530; [Hg-2(Pym)](ClO4)(2): orthorhombic, Pnma, Z = 4, a = 1182.7(2), b = 1662.5(2), c = 607.9(1) pm, R-all = 0.0438; [Hg-2(Pyp)(2)](ClO4)(2): orthorhombic, Aba2, Z = 4, a = 1529.39(9), b = 1047.10(14), c = 1133.49(15) pm, R-all = 0.0381. The crystal structures of [Hg-2(Pym)](NO3)(2) and [Hg-2(Pym)](ClO4)(2) contain polymeric cationic chains [Hg-2(Pym)](+) that are arranged to corrugated layers between which the anions are situated. [Hg-2(Pyp)(2)](ClO4)(2) consists of polymeric cationic layers that are built from (Hg-2)(2)(Hg-2)(2/2)(Pyp)(4) rings connected to each other; the perchlorate tetrahedra are located between these layers.

The solution structure of 1:2 phenol/N-methylpyridinium bis{(trifluoromethyl)sulfonyl}imide liquid mixtures

Neutron diffraction has been used to investigate the liquid structure of a 1:2 solution of phenol in the ionic liquid N-methylpyridinium bis{(trifluoromethyl)sulfonyl}imide at 60 ◦C, using the empirical potential structure refinement (EPSR) process to model the data obtained from the SANDALS diffractometer at ISIS. Addition of phenol results in suppression of the melting point of the pyridinium salt and formation of a room temperature solution with aromatic phenol–cation and phenol-OH to anion hydrogen-bonding interactions.