The remote hydroxyl functional group induced structural diversities in benzimidazolin-2-chalcogenone complexes of antimony(III) have been investigated. The hydroxyl functionalized imidazole chalcogenone based antimony(III) halides have been synthesized and characterized by FT-IR, 1H and 13C NMR, TGA, CHNS, UV–visible, Raman and single-crystal X-ray diffraction techniques. The structural investigation reveals that the dinuclear [{(μ2-L1/L2)SbX2(μ2-X)}2]∞ (L1 = 1-(2-hydroxyethyl)-3-isopropyl-benzimidazole-2-selenone; L2 = 1-(2-hydroxyethyl)-3-isopropyl-benzimidazole-2-selenone; X = Cl or Br) core in the coordination polymer forms an Sb(III) chalcogenone corrugated coordination layer through strong intermolecular coordination, which is triggered by the hydroxyl functional group of the ligand. The central metal ion shows a distorted octahedral geometry. The Hirshfeld surface analysis was mapped using pseudo-mirrored 2D fingerprint plots to study the short interatomic distances in the crystal structure. The major short inter-atomic distances are covered by H····X and H····H in the Hirshfeld surfaces. © 2022 Elsevier Ltd