Hybrid Framework Iron(II) Phosphate-Oxalates
Two inorganic - organic hybrid framework iron phosphate-oxalates, I, [N2C4H12]0.5[Fe2(HPO 4)(C2O4)1.5] and II, [Fe2(OH2)PO4(C2O4) 0.5], have been synthesized by hydrothermal means and the structures determined by X-ray crystallography. Crystal Data: compound I, monoclinic, spacegroup = P21/c (No. 14), a = 7.569(2) Å, b = 7.821(2) Å, c = 18.033(4) Å, β = 98.8(1)°, V = 1055.0(4) Å3, Z = 4, M = 382.8, Dcalc = 2.41 gcm-3, MoKα, F = 0.02; compound II, monoclinic, spacegroup = P21/c (No. 14), a = 10.240(1) b = 6.375(3) Å, c = 9.955(1) Å, β = 117.3(1)°, V = 577.4(1) Å3, Z = 4, M = 268.7, Dcalc = 3.09 g cm-3, MoKα, AF = 0.03. These materials contain a high proportion of three-coordinated oxygens and [Fe2O9] dimeric units, besides other interesting structural features. The connectivity of Fe2O9 is entirely different in the two materials resulting in the formation of a continuous chain of Fe-O-Fe in II. The phosphate - oxalate containing the amine, I, forms well-defined channels. Magnetic susceptibility measurements show FeII to be in the high-spin state (t4 2ge2 g) in II, and in the intermediate-spin state (t5 2ge1 g) in I.
A. Choudhury et al., "Hybrid Framework Iron(II) Phosphate-Oxalates," Journal of Solid State Chemistry, vol. 146, no. 2, pp. 538-545, Elsevier, Sep 1999.
The definitive version is available at https://doi.org/10.1006/jssc.1999.8428
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