Hybrid framework iron(II) phosphate-Oxalates

Choudhury, Amitava ; Natarajan, Srinivasan ; Rao, C. N. R. (1999) Hybrid framework iron(II) phosphate-Oxalates Journal of Solid State Chemistry, 146 (2). pp. 538-545. ISSN 0022-4596

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Official URL: http://linkinghub.elsevier.com/retrieve/pii/S00224...

Related URL: http://dx.doi.org/10.1006/jssc.1999.8428


Two inorganic-organic hybrid framework iron phosphate-oxalates, I, [N2C4H12]0.5[Fe2(HPO4)(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 g cm-3, MoKα, RF=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, RF=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 (t42ge2g) in II, and in the intermediate-spin state (t52ge1g) in I.

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