Three derivatives of benzimidazole have been synthesized and characterized based on 1H and 13C NMR, FTIR, FAB-mass and UV spectra, and the structures of two compounds are characterized based on single crystal XRD studies. Existence of both interand intra-molecular hydrogen bonds has been identified in the case of 2-(o-aminophenyl)benzimidazole amine and not in case of N-methyl-2-(o-nitrophenyl)benzimidazole. While the former is a completely planar molecule, the latter is not. Both the compounds exhibit interesting lattice structures.