The tribenzosilatrane moiety has been substituted with four long paraffinic chains. The physicochemical properties (optical microscopy, differential scanning calorimetry) of the condensed phases have been determined as a function of the chain length. Several crystalline or mesomorphic phases have been characterized by X-ray diffraction. In some cases, original layered structures have been found with a hexagonal order within the lamellae. However, none of the mesophases can be attributed to the class of plastic crystals. A globularity criterion has been defined which relates the shape of the molecular unit with the type of arrangement in the mesophases.