Issue 12, 2001

Abstract

A new manganese molybdenum(V) hydroxyphosphate, Na15Mn10[(HPO4)(PO4)3Mo6O12(OH)3]4(PO4)·48H2O (1), based on the {MnII[P4Mo6O28(OH)3]2}16− building block has been synthesized hydrothermally and its structure solved by single-crystal X-ray diffraction. Its structure consists of linear manganese phosphate tetramers with edge sharing manganese octahedra. Four tetramers are connected via a phosphato group lying on a [4 with combining macron] axis, leading to infinite chains of manganese to which {MnII[P4Mo6O28(OH)3]2}16− anions are anchored. The variable temperature magnetic susceptibility data for 1 were fitted with a model taking into account only magnetic interactions arising betweeen manganese sharing oxygen atoms. Thus, the spin Hamiltonian ĤS = −J1(Ŝ1Ŝ2 + Ŝ3Ŝ4) − J2Ŝ2Ŝ3 was used, and the best fit was found for g = 2.018, J1 = −1.09 cm−1 and J2 = −3.65 cm−1, showing the antiferromagnetic character of the exchange interactions in 1. Attempts to obtain the analogous cobalto compound led to the cobalt molybdenum(V) phosphate Na12Co3[(PO4)4Mo6O12(OH)3]2·44H2O (2). 1 and 2 present two radically different three-dimensional structures. In 2, the {Co[P4Mo6O28(OH)3]2}16− units are connected via monomeric Co2+ in an octahedral environment to give a three-dimensional framework, with long Co2+–Co2+ distances. The sodium counter-ions are located in tunnels running along the [001] and [010] axes. This clearly shows that the three-dimensional structure is determined by the nature of the transition metal.

Graphical abstract: Synthesis, crystal structure and magnetic properties of new molybdenum(v) phosphates containing Mn2+ or Co2+ with three-dimensional structures directed by the nature of the transition metal

Supplementary files

Article information

Article type
Paper
Submitted
08 May 2001
Accepted
08 Aug 2001
First published
20 Sep 2001

J. Mater. Chem., 2001,11, 3392-3396

Synthesis, crystal structure and magnetic properties of new molybdenum(V) phosphates containing Mn2+ or Co2+ with three-dimensional structures directed by the nature of the transition metal

C. D. Peloux, P. Mialane, A. Dolbecq, J. Marrot, E. Rivière and F. Sécheresse, J. Mater. Chem., 2001, 11, 3392 DOI: 10.1039/B104030H

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