The temperature and enthalpy vs composition phase diagrams of the binary systems [xC(2)H(5)CO(2)Li + (1 - x)C2H5CO2TI], and [x(n-C4H9CO2Li) + (1 - x)n-C4H9CO2TI], where x is the mole fraction, were determined by DSC. Both binary systems display the formation of one 2.1 mixed salt each (at x = 0.667) that appear as a peritectic (incongruent melting) at T-fus = 512.0 K, and T-fus = 461.1 K. with Delta H-fus(m) = 13.76 and 8.08 kJ.mol(-1) for Li-TI (1) propanoates, and n-pentanoate mixed salts, respectively The thermotropic liquid crystal of the thallium(1) n-pentanoate transforms into a more stable liquid-crystal phase, which appears in the phase diagram between 380 and 488 K and for x = 0 up to lambda = 0 56 The crystal structure of thallium(I) propanoate and of the two mixed salts were obtained via X-ray synchrotron radiation diffraction measurements. These compounds present a bilayered structure similar to the two pure lithium salts previously found by our group