Abstract We have found that some bowl-like compounds can form disordered crystalline phaseswhich have long-range positional order, with strong fluctuation in position and orientation. Their side chains are in a molten state. X-ray diffraction has shown that two homologues of hexaesters of cyclotricatechylene are stacked as triclinic system with space group of Pl. The parameters of a unit cell, density of the compounds, as well as expansion coefficient are obtained. The modelling of an unit cell is presented, which confirms the up and down asymmetry in the molecules, but there is no ferroelectricity macroscopically.