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Supramolecular association via Sb...S and C—H...S interactions in dimeric tris ( N , N ‐dimethyldithiocarbamato‐ S , S ′)antimony(III): an approach to overcome the concept of steric bulk on such interactions
Author(s) -
Chauhan H. P. S.,
Carpenter Jaswant
Publication year - 2013
Publication title -
acta crystallographica section b
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.604
H-Index - 33
eISSN - 2052-5206
pISSN - 2052-5192
DOI - 10.1107/s2052519213029618
Subject(s) - chemistry , steric effects , hydrogen bond , supramolecular chemistry , aryl , dimer , alkyl , molecule , dithiocarbamate , stereochemistry , crystallography , morpholine , crystal structure , medicinal chemistry , organic chemistry
Tris ( N , N ‐dimethyldithiocarbamato‐ S , S ′)antimony(III) has been isolated as a dimer in acetonitrile. Single‐crystal X‐ray analysis shows that the molecule possesses both Sb...S and C—H...S interactions, which results in a supramolecular association in the absence of hydrogen‐bonding functionality on the R group. The co‐existence in the title compound of such interactions is a unique character of known dimeric antimony(III) alkyl and/or aryl dithiocarbamate complexes. The literature reveals that the species where the alkyl and/or aryl dithiocarbamates carry the following groups: R = methyl (chloroform solvated), ethyl, n ‐propyl, pyrrolidine, morpholine, piperidine, azepane, benzyl, methylphenyl, are not capable of forming significant hydrogen‐bonding interactions. However, either Sb...S or C—H...S intermolecular interactions dominate between two centrosymmetrically related molecules leading to a supramolecular aggregation. In the species where the R group carries hydrogen‐bonding functionality, i.e. 2‐hydroxylethyl, the C—H...S interactions are subverted by O—H...O hydrogen bonding. In addition, the title compound does not have steric hindrance or any hydrogen‐bonding group but is stabilized with the co‐existence of Sb...S and C—H...S interactions. Analysis of the secondary interactions of a series of analogues previously reported reveals that steric bulk is unnecessary for the mitigation of Sb...S interactions and for the establishment of C—H...S secondary bonding.