Formation of supramolecular complexes in reactions of adduct formation of zinc diethyldithiocarbamate with morpholine. Molecular structures and thermal properties

A supramolecular compound of the general formula [Zn{NH(CH2)4O} {S2CN(C2H5)2}2]4 · NH(CH2)4O · C2H4{N(CH2)4O}2 (I) was obtained and examined by X-ray diffraction analysis and thermography. According to X-ray diffraction data, the crystal lattice of compound I shows an unusual alternation of two independent centrosymmetric supramolecular complexes [Zn{NH(CH2)4O} {S2CN(C2H5)2}2]2 · C2H4{N(CH2)4O}2 (Ia) and [Zn{NH(CH2)4O} {S2CN(C2H5)2}2]2 · NH(CH2)4O (Ib). Either complex includes two molecules of an adduct of bis(diethyldithiocarbamato)zinc with morpholine and outer-sphere molecules of 1,2-dimorpholinoethane or morpholine. Adduct molecules are structurally nonequivalent in pairs and linked with solvate molecules by hydrogen bonds. The calculated geometries of the zinc polyhedra are intermediate between trigonal bipyramid and tetragonal pyramid. Thermal decomposition of supramolecular compound I proceeds through desorption of the outer-sphere and coordinated organic molecules; in the final step, defragmentation of the dithiocarbamate part gives zinc sulfide.