Synthesis and structural characterization of some adducts of 1,4-dithian and -oxathian with silver(I) nitrate and perchlorate

摘要

Despite its relatively high melting point of 112 deg C, 1,4-dithian (S(CH_2CH_2)_2S = L) sublimes readily and malodorously at ambient temperatures,a factor possibly influential in the limited use it has found as a ligand despite its simplicity; the disposition of the sulfur atoms also may be such as to encourage the formation of perhaps uncongenial oligomers/polymers, rather than chelating to the same atom, even in 'boat' conformations. Its crystal structure was determined in 1955 and there appears to be no subsequent redetermination using improved techniques, or, until recently, seemingly very few metal complexes. Accordingly, we have initiated a minor foray into this area with a redetermination of the structure of the parent ligand and two complexes obtained by co-crystallization with silver(I) oxyanion salts (nitrate and perchlorate) from acetonitrile solution. We record this work herein. Contemporaneous studies have recently recorded the structural characterization of a number of AgX/dithian adducts of various stoichiometries, but neither of the present, although a synthesis of the nitrate is reported and the tetrafluoroborate is isomorphous with the perchlorate. We also report a redetermination of enhanced precision for the adduct of 1:1 stoichiometry of silver(I) nitrate with 1,4-oxathian (O(CH_2CH_2)_2S), with a reinterpretation in terms of a two-dimensional sheet structure.