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The crystal and molecular structures of {Zn[S 2 CN(CH 2 CH 2 OH) 2 ] 2 } 2 (pyrazine), ( 1 ), and its di-dioxane solvate, ( 2 ), are described. In each of these, the centrosymmetric, binuclear molecule features a five-coordinated, highly distorted square-pyramidal geometry based on a NS 4  donor set. The three-dimensional architectures in  1  and  2  are sustained by extensive networks of distinctive hydroxyl-O–H···O(hydroxyl) hydrogen bonding. The topology of the lattices are very different with that of  2  having a more regular appearance. The dioxane molecules reside in channels defined by the host molecules in  2  but, do not make many significant interactions with the host. The fact that  1  exhibits a significantly greater packing efficiency and a higher density suggests  1  is more stable than  2 . The retention of dioxane in crystals of  2  probably reflects its intimate involvement in nucleation and high boiling point, meaning it is retained during crystallisation. Hirshfeld surface analyses were conducted and confirm the importance of the hydroxyl-O–H···O(hydroxyl) hydrogen bonding but, also reveal the presence of other interactions, most notably C–H···π(chelate) interactions.

Supramolecular association in (μ 2 -pyrazine)-tetrakis(N,N-bis(2-hydroxyethyl)dithiocarbamato)dizinc(II) and its di-dioxane solvate