We report on three different liquid crystalline compounds with a central septithiophene core and alkylated end groups of strongly increasing bulkiness. In principle, the thiophene cores prefer to pack parallel to optimize their pi-pi interactions, which becomes sterically impossible for the bulkier end groups. Using X-ray diffraction, we find that the way out of this packing dilemma is toward liquid-crystal phases of higher dimensionality in the order smectic -> columnar <-> bicontinuous cubic. For the smectic phase, packing in a monolayer is no problem; for the other ones packing considerations become more stringent in films due to the boundaries. Surface X-ray techniques and atomic force microscopy indicate an appreciable difference between monolayer and three-layer films, in which the monolayers appear to escape from packing frustration by generating superstructures. We propose a basic structure of columns parallel to the substrate that provides a compromise between preserving some pi-pi it interactions and packing the bulky alkyl groups.