Some solid and crystalline materials derived from the reactions of diorganotin(IV) with salicylaldehyde- and 3-methoxysalicylaldehyde- substituted aliphatic and aromatic Schiff's bases have been synthesized at room temperature. The 1:1 and 1:2 molecular adducts thus obtained have been characterized by elemental analyses, differential scanning calorimetry and NMR spectroscopic techniques which indicated that the coordination to tin occurs through the hydroxyl oxygen. The single crystals of 1:1 and 1:2 (tin:Schiff's base) diphenyltin(IV) and dibutyltin(IV) adducts with 6-methoxy-l-[(4-cyanophenylimino)methyl]phenol and (2- (phenylethylimino)methyl) phenol have been carried out using the charged-coupled device (CCD) area detector and four-circle diffractometers, respectively. The geometries about the Sn atom in both 1:1 and 1:2 materials are trigonal bipyramidal and octahedral. The DSC spectra of the adducts possessing the long alkoxylated group at the lateral position appear to suggest the existence of liquid crystal/isotropic liquid biphasic region.