Acta Crystallographica Section B

Structural Science, Crystal Engineering and Materials

Volume 70, Part 1 (February 2014)

crystal engineering

Acta Cryst. (2014). B70, 28-36    [ doi:10.1107/S2052520613034781 ]

Metal-organic frameworks based on uranyl and phosphonate ligands

B. Monteiro, J. A. Fernandes, C. C. L. Pereira, S. M. F. Vilela, J. P. C. Tomé, J. Marçalo and F. A. Almeida Paz

Abstract: Three new crystalline metal-organic frameworks have been prepared from the reaction of uranyl nitrate with nitrilotris(methylphosphonic acid) [H6nmp, N(CH2PO3H2)3], 1,4-phenylenebis(methylene)diphosphonic acid [H4pmd, C6H4(PO3H2)2], and (benzene-1,3,5-triyltris(methylene))triphosphonic acid [H6bmt, C6H3(PO3H2)3]. Compound [(UO2)2F(H3nmp)(H2O)]·4H2O (I) crystallizes in space group C2/c, showing two crystallographically independent uranyl centres with pentagonal bipyramidal coordination geometries. While one metal centre is composed of a {(UO2)O3([mu]-F)}2 dimer, the other comprises an isolated {(UO2)O5} polyhedron. Compound [(UO2)(H2pmd)] (II) crystallizes in space group P21/c, showing a centrosymmetric uranyl centre with an octahedral {(UO2)O4} coordination geometry. Compound [(UO2)3(H3bmt)2(H2O)2]·14H2O (III) crystallizes in space group P\bar 1, showing two crystallographically independent uranyl centres. One uranyl centre is a {(UO2)O5} pentagonal bipyramid similar to that in (I), while the other is a {(UO2)O4} centrosymmetric octahedron similar to that in (II). Compounds (I) and (III) contain solvent-accessible volumes accounting for ca 23.6 and 26.9% of their unit-cell volume, respectively. In (I) the cavity has a columnar shape and is occupied by disordered water molecules, while in (III) the cavity is a two-dimensional layer with more ordered water molecules. All compounds have been studied in the solid state using FT-IR spectroscopy. Topological studies show that compounds (I) and (III) are trinodal, with 3,6,6- and 4,4,6-connected networks, respectively. Compound (II) is instead a 4-connected uninodal network of the type cds.

CCDC references: 978938, 978939 and 978940

Keywords: uranyl ligands; metal-organic frameworks; phosphonate ligands.

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Structure factor file (CIF format) (260.1 kbytes)
[ doi:10.1107/S2052520613034781/bi5030Isup2.hkl ]
Contains datablock I

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Structure factor file (CIF format) (121.6 kbytes)
[ doi:10.1107/S2052520613034781/bi5030IIsup3.hkl ]
Contains datablock II

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Structure factor file (CIF format) (223.4 kbytes)
[ doi:10.1107/S2052520613034781/bi5030IIIsup4.hkl ]
Contains datablock III


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