This study discusses the synthesis of two new 2-hydroxyethyl substituted N-heterocyclic carbene (NHC) precursors. The NHC precursors were prepared from 1-(alkyl/aryl)benzimidazole and alkyl halides. They were characterized using H-1 NMR, C-13 NMR, FT-IR, UV-Vis spectroscopy, and elemental analysis techniques. Molecular and crystal structures of 1 and 2 were determined using the single-crystal X-ray diffraction method. Crystal structure of the compounds features NHC precursors and chloride anions. Additionally in 2, the asymmetric unit has a water molecule, which forms a tetrameric chloride-hydrate assembly with the chloride anion. The chloride anions play an important role in the stabilization of crystal structures to form a two-dimensional supramolecular architecture. The 3D Hirshfeld surface and the associated 2D fingerprint plots were also drawn to gain insights into the behavior of the interactions in the compounds.