[2-(Me2NCH2)C6H4]SnCl3 (1) was prepared via (i) salt elimination reaction between RLi and SnCl4 (1:1 molar ratio), in toluene solution, and (ii) redistribution reaction between [2-(Me2NCH2)C6H4]4Sn and SnCl4 (1:3 molar ratio), in the absence of a solvent. Recrystallization from DMSO afforded the isolation of the DMSO adduct [2-(Me2NCH2)C6H4]SnCl3·DMSO (1a). The compounds were characterized by multinuclear NMR (1H, 13C, 119Sn) in solution. The molecular structures of 1 and 1a were determined by single-crystal X-ray diffraction. The crystal structure of compounds 1 and 1a consists of discrete monomeric molecular units separated by normal van der Waals distances between heavy atoms. The N atom of the pendant CH2NMe2 arm is strongly coordinated to the tin atom, thus resulting in distorted trigonal bipyramidal (C,N)SnCl3 and octahedral (C,N)SnCl3O cores for 1 and 1a, respectively. For both compounds hydrogen bonding generates supramolecular associations in crystal. Copyright © 2005 John Wiley & Sons, Ltd.