Liquid crystalline properties of the synthesized liquid crystal (LC) N-(o-hydroxybenzylidene)-N′-(4-n-alkoxybenzylidene) azines (HBDBA) are probed thoroughly using the comprehensive array of techniques e.g. differential scanning calorimetry (DSC), differential thermal analysis (DTA), polarizing optical microscopy (POM), temperature-dependent Raman spectroscopy and density functional theory (DFT) method. In this study, intricate molecular interactions crucial for mesophase formation of liquid crystalline system HBDBA and molecular rearrangement that occurs during LC transitions are unravelled comprehensively. Remarkably, at the Cr → SmA phase transition, the peak position, linewidth, and intensity of signature Raman bands are prominently changed. A thorough analysis of Raman marker bands and DFT calculation confirm the disruption of intramolecular hydrogen bonds in HBDBA at the Cr → SmA transition. The conclusion of the present study enriches the understanding of the underlying mechanisms of mesophase formation and intricate molecular interactions and arrangement at the molecular level of the thermotropic LC.