Design and understanding of solid-state and crystalline materials
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CrystEngComm, 2006, 8, 104 - 118, DOI: 10.1039/b517339f
Aggregation patterns in the crystal structures of organometallic Group XV 1,1-dithiolates: the influence of the Lewis acidity of the central atom, metal- and ligand-bound steric bulk, and coordination potential of the 1,1-dithiolate ligands upon supramolecular architecture
Edward R. T. Tiekink
Supramolecular association operating in the crystal structures of organo-phosphorus, -arsenic, -antimony and -bismuth 1,1-dithiolate compounds is surveyed with the purpose of delineating the factors that dictate the formation of the resultant range of aggregates. Primary considerations for the formation of secondary M
S interactions relate to the Lewis acidity of the central atom that can be moderated by i) the nature of the metal atom itself, e.g. the Lewis acidity of P < As < Sb < Bi, ii) the number of metal-bound organic substituents, e.g. the Lewis acidity of R2M < RM, and iii) the coordination potential of the 1,1-dithiolate ligand, e.g. the Lewis acidity of M(S2CNR2) < M(S2COR). Another vital factor is the steric profile of the metal- and/or ligand-bound R groups, i.e. when R is large, MS interactions are precluded. When MS interactions are absent, for whatever reason, the crystal packing is invariably dominated by C–HS interactions that usually lead to chain motifs.
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