In this work, we describe a simple and efficient route for the synthesis of novel N1-substituted benzimidazole derivatives (8-14) by a rearrangement reaction of N1-alkyl-1,5-benzodiazepine-2-thiones (1-7) in the presence of hydroxylamine hydrochloride in boiling ethanol. Good to excellent yields were achieved for a wide range of alkyl partners with both short-chain and long-chain substituents. The title products were identified using H-1 and C-13-NMR spectroscopic measurements and confirmed by single-crystal X-ray diffraction techniques for 8-10. In addition, we performed theoretical studies of 8-10 using Hirshfeld surface analysis, molecular docking studies and, along with experimental data. The predicted spectral data were obtained using density functional theory (DFT) at the B3LYP/6-311++G(d,p) level of theory. Also, according to Monte Carlo simulations, the inhibition trend is 10 > 8 > 9 toward all metals in an acidic environment. Good inhibition performance is predicted for iron as compared to copper and aluminum metals.