In this research, four hybrid materials, namely [Ni(MC)]₃[VO₃]₆·12.25H₂O (1), [Cu(MC)]₃[VO₃]₆ (2), [Ni(PC)]₃[VO₃]₆·2H₂O (3), and [Cu(PC)]₃[VO₃]₆·2H₂O (4) (MC = 1,8-dimethyl-1,3,6,8,10,13-hexaazacyclotetradecane, PC = 1,8-dipropyl

-1,3,6,8,10,13-hexaazacyclotetradecane), were obtained by reacting transition metal macrocyclic complexes with NH₄VO₃. Subsequently, they were characterized by physico-chemical and spectroscopic methods, and X-ray powder diffraction. Single-crystal structure analysis revealed that the Ni(II)/Cu(II) atoms were coordinated by two oxygen atoms from [VO₄] tetrahedra and four nitrogen atoms from ligands, thereby forming a six-coordinate octahedral coordination geometry. Six [VO₄] tetrahedra form a hexanuclear [V₆O₁₈]⁶⁻ ring by sharing six μ₂-oxygen atoms in complexes 1–4. All complexes exhibited similar three-dimensional structures formed by connections of hexanuclear [V₆O₁₈]⁶⁻ rings with their corresponding cationic moieties.