3D-, 2D- and 1D-supramolecular structures of {Zn[S2CN(CH2CH2OH)R]2}2 and their {Zn[S2CN(CH2CH2OH)R]2}2(4,4′-bipyridine) adducts for R = CH2CH2OH, Me or Et: polymorphism and pseudo-polymorphism

Abstract

Supramolecular aggregation in the binary zinc dithiocarbamates, in which the dithiocarbamate ligands carry hydrogen-bonding functionality, i.e. {Zn[S2CN(CH2CH2OH)R]2}2, leads to 3D-, 1D- and 2D-architectures for R = CH2CH2OH, Et and Me, respectively. For R = CH2CH2OH, two polymorphs are found, both with 3D-network structures, but constructed from undulating (orthorhombic form) or flattened (monoclinic) layers. Linear chains are found for R = Et where molecules associate head-to-head. The intervention of solvent methanol in the R = Me structure provides additional links between molecules to allow the formation of a 2D-array. In their 4,4-bipyridine adducts, {Zn[S2CN(CH2CH2OH)R]2}2(4,4′-bipyridine), 3D-, 1D- and 2D-architectures are also found. 3D-networks are found for the R = CH2CH2OH and Et derivatives. For the latter compound, solvent methanol in its pseudopolymorph disrupts the 3D-network so that a 1D-supramolecular chain is found. Finally, in the R = Me structure, orthogonally inclined 2D-arrays are interpenetrated to form a 3D-network.