One dimensional iron molybdophosphate anionic chains with different structural arrangements reflecting a flexibility character

Abstract

Structural comparison of a new compound [(bpp)₃H₆]Fe₂ ^IIIFe₂ ^IIMo₂₄ ^V(H₂PO₄)₈(HPO₄)₄(PO₄)₄O₄₈(OH)₁₂· (H₂O)₄·2H₂O(1)[bpp=1,3-di(4-pyridyl)propane] with our previously reported two compounds [(bpy)₃Fe^II]₃sdFe₂ ^IIIFe₂ ^IIMo₂₄ ^V(H₂PO₄)₈(HPO₄)₄(PO₄)₄O₄₈(OH)₁₂(H₂O)₄·12H₂O(2) and [(bpy)₃Fe^II]₂Fe^IIFe^IIIMo₁₂ ^V(H₂PO₄)₂(H_2−xPO₄)·(H_1+xPO₄)(HPO₄)₂(PO₄)₂O₂₄(OH)₆(H₂O)₂·9H₂O(x=0-21)(3)(bpy=2,2′-bipyridine), which all exhibit one-dimensional mixed-valence iron molybdophosphate anionic chains constructed by alternating connection of Fe^III ions and magic [Fe^II(Mo₆P₄O₃₁)₂] units, reveals that the non-hydrogen atomic ratios of Mo:Fe:P:O within the polymeric anionic chains are the same for all the three compounds, while the polymeric anionic chains of the different compounds bear different numbers of negative charges. And therefore there exist different numbers of counter cations per {Fe₂ ^III[Fe₂ ^II(P₁₆Mo₂₄ ^VO₁₂₄)]} unit found in the titled compounds. It discloses that not only are the spatial assembling of counter cations and polymeric inorganic chains of three compounds quite different, but also the O—Fe^III—O bond angles and Fe^III—O bond lengths of the three different inorganic chains exhibit small differences. What is more important is that such small changes in bond length and bond angle in the assemblage of Fe^III—O bonds lead to the considerable fluctuations of inorganic chains in their structural conformation within the three compounds, reflecting an interesting phenomenon of “flexibility” in the pure inorganic one dimensional mixed-valence iron molybdophosphate chains.

Keywords

Flexibility / Conformation / Crystal structure / Inorganic chain / Iron molybdophosphate

References

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