A Versatile Polyoxovanadate in Diverse Cation Matrices: A Supramolecular Perspective

A series of decavanadate based compounds, formulated as [Co(H₂O)₆][{Na₄(H₂O)₁₄}{V₁₀O₂₈}]·4H₂O (1), [Zn(H₂O)₆][Na₃(H₂O)₁₄] [HV₁₀O₂₈]·4H₂O (2), [HMTAH]₂ [{Zn(H₂O)₄}₂{V₁₀O₂₈}]·2H₂O (3), [{Co(3-amp)(H₂O)₅}]₂ [3-ampH]₂ [V₁₀O₂₈] · 6H₂O (4), [4-ampH]₁₀[{Na(H₂O)₆}{HV₁₀O₂₈}][V₁₀O₂₈]·15H₂O (5), [{4-ampH}₆ {Co(H₂O)₆}₃][V₁₀O₂₈]₂·14H₂O (6), and [{4-ampH}₁₀{Zn(H₂O)₆}][V₁₀O₂₈]₂·10H₂O (7), have been synthesized (where HMTAH = mono-protonated hexamethylenetetramine, 3-ampH = protonated 3-amino pyridine and 4-ampH= protonated 4-aminopyridine) from the relevant aqueous sodium-vanadate solution, by varying the pH of the solution and amino pyridine/hexamine derivatives as well as transition metal salts (Co(II)- and Zn(II)-salts). In this series of compounds 1-7, the polyoxovanadate (POV) cluster [V₁₀O₂₈]^6- is the common cluster anion, stabilized by diverse cations. The diverse supramolecular patterns around the decavanadate cluster anion in different cationic matrices have been described to understand the microenvironment in the decavanadate-based minerals. All of these compounds have solvent water molecules in their respective crystal lattices. Since water can interact directly with cations and anions, providing an additional stability and structural diversity, we have analyzed supramolecular water structures in all these compounds to comprehend the role of the lattice water in the formation of natural decavanadate containing minerals. Compounds 1-7, that are isolated at an ambient condition from aqueous solution, are characterized by routine spectral analysis, elemental analyses and finally unambiguously by single crystal X-ray crystallography.