Six new diorganotin(IV) complexes of the type (R 2 Sn) 2 L (L=L1 R=Me 1, nBu 2; L=L2 R=Me 3, nBu 4; L=L3 R=Me 5, nBu 6) have been obtained by the reaction of new hexadentate diacylhydrazone ligands H 4 L1 [bis(2-hydroxybenzaldehyde)terephthalohydrazone], H 4 L2 [bis(2-hydroxy-3-methoxybenzaldehyde)terephthalohydrazone] or H 4 L3 [bis(2-hydroxy-1-naphthaldehyde)terephthalohydrazone] with diorganotin(IV) dichloride in the presence of sodium ethoxide. All the diacylhydrazones and the complexes were characterized by elemental analysis, IR and NMR spectra. Complexes 2, 4, 5 and 6 were also characterized by X-ray crystallography diffraction analysis which revealed that the complexes have similar structures containing binuclear diorganotin(IV) skeletons. Furthermore weak but significant intermolecular Sn⋯O bonds, hydrogen bonds, C–H⋯π stacking or π⋯π stacking lead to aggregation and assembly of these complexes into 1D, 2D or 3D supramolecular frameworks.