The outcomes of reactions of Cu(II) salts with 2-iodobenzoic acid (2-IBA) in acetonitrile in presence of different substituted pyridines (Py, 4-MePy, 4-EtPy, 3,4-MePy, 2,6-MePy, 2,4,6-MePy and 2,6-BrPy) (L) depend on the nature of Cu-containing precursors and L, resulting in [Cu₂(2-IBA)₄(CH₃CN)₂], [Cu₂(2-IBA)₄L₂] or [Cu₂L₄(2-IBA)₂Cl₂] complexes. In total, seven complexes were prepared and characterized by X-ray diffractometry. The role of halogen bonding (XB) in the structures was examined by theoretical methods.