Calorimetric and X-ray powder diffraction studies of N-(4-n-butyloxybenzylidene)-4'-n'-octylaniline are presented. Heat capacity measurements have been performed by adiabatic calorimetry in the temperature range from 5 K to 375 K. Three liquid crystalline phases, i.e., nematic, smectic A and smectic B, and an ordered crystal of triclinic structure and two new metastable crystal phases were observed. In addition, the crystalline smectic B phase of different sequence of molecular layers than liquid crystalline smectic B, has been found. Both smectic B phases have been vitrified. For the smectic B phase a hexagonal unit cell has been identified by X-ray diffraction. The diffraction pattern of glass of crystalline smectic B phase is shown.