Organotin(N) compounds of the type [(o-MeEC6H4)CH2](2)SnPh2-nCln were synthesized, E = O, n = 0 (1), n = 1 (2), and n = 2 (3); E = S, n = 0 (4), n = 1 (5), and n = 2 (6); and E = CH2, n = 0 (7), n = 1 (8), and n = 2 (9). The dichloro compounds 3 and 6 have been investigated by single-crystal X-ray diffraction and exhibit bicapped tetrahedral geometry at the tin atom as a consequence of significant intramolecular Sn center dot center dot center dot O (3) and Sn center dot center dot center dot S (6) secondary bonding, in monomolecular units. Compound 3, when crystallized from a hexane/THF solvent mixture, shows two different conformers, 3' and 3 '', in the crystal structure; 3' has two equivalent Sn center dot center dot center dot O interactions, while 3 '' has two nonequivalent Sn center dot center dot center dot O interactions. Upon the recrystallization of 3 from hexane, only a single structural form is observed, 3'. The Sn center dot center dot center dot E distances in 3', 3 '', and 6 are 71.3, 73.5 and 72.9, and 76.3% of the Sigma vd radii, respectively. The meta- and para-substituted isomers of 3 (10, 11) exhibit a distortion at the tin atom due to self-association via intermolecular Sn center dot center dot center dot Cl interactions, resulting in polymeric structures. Sn-119 NMR spectroscopy suggests that the intramolecular Sn center dot center dot center dot E interactions persist in solution for the dichloride compounds 3 and 6.