This work describes the synthesis, molecular structure, and packaging of the compounds 6-bromo-2,3-dimethoxybenzaldehyde (6-BRB) and 5-bromo-2,3-dimethoxybenzaldehyde (5-BRB). Characterization in the solid-state was carried out by X-ray diffraction, and the analysis of the interactions was described by the Hirshfeld surface, which helps in understanding the effect of replacing the bromine position in the aromatic ring. Both compounds (6-BRB and 5-BRB) crystallized in the space group P21/c and are stabilized with C–HO interactions, but only the 6-BRB has a halogen-type interaction. Theoretical calculations, carried out by the density functional theory at the CAM-B3LYP/6-311++G(d,p) level of theory in gas phase, provided information on their electronic properties. The geometric properties were compared to experimental data, and the analyses of the frontier molecular orbitals and the molecular electrostatic potential (MEP) maps were obtained to predict the physical-chemical properties. The supramolecular arrangements were analyzed throughout complexation interactions and corrected by counterpoise method. Hyperconjugation energies were employed to examine the stability of the intermolecular interactions of the compounds. The interaction intensities were determined through the topological parameters obtained through the quantum theory of atoms in molecules model.