Symmetrically and unsymmetrically N, N '- substituted benzimidazolin-2- stannylenes with sterically nondemanding alkyl ( Me and Et) and Lewis base functional groups ( -( CH2) n OMe, -( CH2) n NMe2; n) 2, 3) have been synthesized by the transamination reaction between suitably substituted o- phenylenediamines and Sn[ N( SiMe3) 2] 2. The N, N'-dimethyl-substituted stannylene 3 exists in the solid state as a bimolecular aggregate which is held together by strong intermolecular Sn center dot center dot center dot N interactions leading to three-coordinated tin atoms. The benzimidazolin- 2- stannylenes with N, N'-( CH2)nOMe substituents ( 5, n) 2; 6, n) 3) exhibit weak intramolecular Sn,,, O interactions in solution. Benzannulated stannylenes with N, N '-( CH2) n NMe2 substituents ( 7, n) 2; 8, n) 3) are again dimers which exhibit both intramolecular Sn center dot center dot center dot NMe2 and intermolecular Sn,,, N interactions, which leads to tri- or tetracoordinated tin atoms. Some unsymmetrically N, N '- substituted benzimidazolin- 2- stannylenes have also been synthesized. The molecular structures of 3, 5, and 8 and the relation between the chemical shift recorded for the tin atoms and the solvent ( C6D6 or THF- d (8)) used for recording Sn-119 NMR spectra will be discussed.