First porous one-dimensional mixed valent iron molybdophosphate

Abstract

A mixed-valence iron molybdenum phosphate of the formula, [(C₁₀H₉N₃)H]₄[Mo₁₂^(V) Fe₂^(III)Fe^(II)O₁₈(HPO₄)₂(PO₄)₆(OH)₁₄(H₂O)₈]·5H₂O, I, has been synthesized hydrothermally in the presence of 2,2'-dipyridylamine. The framework structure consists of a network of MoO₆, FeO₆ octahedra and PO₄ tetrahedra. The connectivity between the polyhedral units form [Fe^II(P₈Mo₁₂^V) discrete building units that are connected by Fe^IIIO₆ octahedra giving rise to one-dimensional chain-like structure with eight-membered apertures. The individual chains units are held together by hydrogen bond interactions forming layers with pores, in which the 2,2'-dipyridylamine molecules are located. This is the first time, to our knowledge, that such one-dimensional structure with voids has been isolated. Crystal data for I: monoclinic, space group C2/m, a=14.5952(2), b=29.7878(5), c=12.69730(10) Å, β=116.5580(10)°, Z=2, V=4937.78(11) ų, F(000)=3446, R₁=0.059, wR₂=0.148 and S=0.985.