The influence of cation upon the supramolecular aggregation patterns of dithiocarbamate anions functionalised with hydrogen bonding capacity-the prevalence of charge-assisted O-H•••S interactions

A range of supramolecular architectures is found in the title dithiocarbamate salts, each with hydrogen bonding functionality in the form of at least one hydroxyl group. A common feature in the crystal packing is the prevalence of charge-assisted O-H center dot center dot center dot S hydrogen bonding. In [NH4][S2CN(CH2CH2OH)(2)] (1), a 3-D network is found mediated by cooperative O-H center dot center dot center dot S, N-H center dot center dot center dot O and N-H center dot center dot center dot S hydrogen bonding. Reducing the hydrogen bonding functionality by replacing the ammonium cation in (1) by the 4-aza-1-azoniabicyclo(2.2.2)octanium cation to give [DABCO-H][S2CN(CH2CH2OH)(2)] (2), results in a 2-D array. Further reduction of the hydrogen bonding functionality, this time by substituting a CH2CH2OH with an alkyl group to give [DABCO-H][S2CN(CH2CH2OH)CH3] (3) and [DABCO-H][S2CN(CH2CH2OH)CH2CH3] (4) allows for the formation of 1-D supramolecular chains. The introduction of alkali metal cations rather than protic cations removes the possibility of the hydroxyl-O participating in hydrogen bonding interactions as these now coordinate the alkali metal. In the sodium trihydrate, Na[S2CN(CH2CH2OH)(2)]center dot 3H(2)O (5), O-H center dot center dot center dot O hydrogen bonds are found along with charge- assisted O-H center dot center dot center dot S contacts so that a 3-D network results. Substituting a CH2CH2OH group with a n-propyl group gives Na[S2CN(CH2CH2OH)CH2CH2CH3]center dot 2H(2)O (6) and yields a 2-D array. For the anhydrous K[S2CN(CH2CH2OH)(2)] (7) and Cs[S2CN(CH2CH2OH)(2)] (8) salts, the crystal packing is dominated by charge- assisted O-H center dot center dot center dot S hydrogen bonding giving 3-D network structures. The systematic analysis of the crystal packing patterns of these salts reveals the importance of charge- assisted O-H center dot center dot center dot S hydrogen bonding in stabilising these crystal structures.