Effect of substituents in the molecular and supramolecular architectures of 1-ferrocenyl-2-(aryl)thioethanonesElectronic supplementary information (ESI) available. CCDC 1044508-1044513 and 1051170. For ESI and crystallographic data in CIF or other electronic format see DOI: 10.1039/c5ce00149h

We discuss here a comprehensive solid state approach to the influence of diverse molecular functionalities present in a group of 1-ferrocenyl-2-(aryl)thioethanones [aryl = phenyl, 2-, 3-, and 4-chlorophenyl, 3- and 4-methoxyphenyl, 4-nitrophenyl, and 2-naphthyl] on their molecular structures, intermolecular contacts and subsequent supramolecular arrangements. Ab initio calculations provide electrostatic charge distributions and electron density isosurface maps to assist this analysis. Atomic point charges are used to evaluate the best acceptors and donors in the molecules. The absence of good hydrogen donors increases the influence of close packing factors on the crystal network for the majority of these compounds. However the characteristics of each substituent, like the donor-acceptor ability of the methoxy group, electronic anisotropy of chlorine or electronic resonance of the nitro group, also play important roles in the self-assembly processes. A systematic and detailed analysis is presented. Relative positioning of substituents in a molecule is determinant in crystal packing of 1-ferrocenyl-2-(aryl)thioethanone derivatives displaying weak hydrogen bonding ability.