The growing importance of crystal engineering and supramolecular chemistry led to interest in the nature of the interactions that bind organometallic molecules into crystals. In part, these interactions are similar to those found in purely organic crystals because the peripheries of these molecules often contain organic residues. Most notable among these intermolecular interactions are hydrogen bonds and aromatic interactions. The aims of crystal engineering are the understanding of intermolecular interactions and their application in the design of crystal structures with specific architectures and properties [1]. An integral part of this work has been a study of the crystal structure and packing interactions of aluminium chelate complexes with the bifunctional ligand EDBP: 2,2’-ethylidenebis(4,6-di-tertbutylphenol). The analysis of structures of these complexes shown that both steric and electronic factors should be taken into consideration. In order to specify the influence of steric and electronic factors on these structures different functional groups around the aluminium centre ranging from alkyl substituent to mono- (1-phenylethanol) and bifunctional ligands (methylthioglycolate, 2metoxyethanol) were used. The crystal structure analysis of these compounds provides interesting data concerning the effect of the nature of ligand and substituents on the molecular assembly of the aluminium complexes. In the case when the solvent molecules were present in the crystal lattice there was also analyzed the role of weak C-H…π interactions. The aryloxide complexes of aluminium were used as model systems to study of the heterocyclic monomers polymerization mechanism.