Synthesis, Crystal Structure, and Properties of Mn(PO3F)(H2O)212. Issue 2 (23rd January 2015)

• Record Type: Journal Article
• Authors: Weil, Matthias; Baran, Enrique J.; Kremer, Reinhard K.; Libowitzky, Eugen
• Is Part Of: Zeitschrift für anorganische und allgemeine Chemie. Volume 641:Issue 2(2015)
• Page Start: 184
• Page End: 191
• Publication Date: 2015-01-23
• Subjects: Chemistry, Inorganic -- Periodicals; Chemistry -- Periodicals; 540
• DOI: 10.1002/zaac.201400587
• Languages: English
• ISSNs: 0044-2313

Abstract

<abstract abstract-type="main" xml:lang="en"> <title>Abstract</title> <p>Single crystals of manganese(II) fluorophosphate dihydrate, Mn(PO<sub>3</sub>F)(H<sub>2</sub>O)<sub>2</sub>, were grown in a metathesis reaction from aqueous solutions of MnCl<sub>2</sub> and (NH<sub>4</sub>)<sub>2</sub>(PO<sub>3</sub>F). The crystal structure [<italic>P</italic><inline-formula><alternatives><tex-math notation="tex"><![CDATA[$\bar{1}$]]></tex-math><inline-graphic xlink:href="ark:/27927/pgh3xswfd4f" mimetype="image" xlink:type="simple" xmlns:xlink="http://www.w3.org/1999/xlink" /></alternatives></inline-formula>, <italic>Z</italic> = 2, <italic>a</italic> = 5.5280(7), <italic>b</italic> = 5.6357(7), <italic>c</italic> = 8.2570(10) Å, <italic>α</italic> = 81.279(2), <italic>β</italic> = 75.156(2), <italic>γ</italic> = 71.722(2)°, 1345 structure factors, 86 parameter, <italic>R</italic>[<italic>F</italic><sup>2</sup> > 2<italic>σ</italic>(<italic>F</italic><sup>2</sup>)] = 0.0322, w<italic>R</italic>(<italic>F</italic><sup>2</sup> all) = 0.0771] consists of [MnO<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>] octahedra that share a common edge to form isolated double octahedra of the type [Mn<sub>2</sub>O<sub>2/2</sub>O<sub>4/1</sub>(H<sub>2</sub>O)<sub>4/1</sub>]. Each double octahedron is bridged by the oxygen atoms of six (PO<sub>3</sub>F) tetrahedra to six neighboring double octahedra into a layered arrangement parallel to (001). Adjacent layers are held together through weak O–H<bold>···</bold>O hydrogen bonds, and no significant hydrogen bonding interactions of the type O–H<bold>···</bold>F are observed. Vibrational spectra are discussed in terms of a site‐symmetry approximation for the (PO<sub>3</sub>F)<sup>2–</sup> anion. The thermal decomposition of Mn(PO<sub>3</sub>F)(H<sub>2</sub>O)<sub>2</sub> starts above 130 °C. In a multi‐stage mechanism the end‐product Mn<sub>2</sub>P<sub>2</sub>O<sub>7</sub> is formed at temperatures above 500 °C. Magnetic measurements suggest an antiferromagnetic ordering of Mn(PO<sub>3</sub>F)(H<sub>2</sub>O)<sub>2</sub> at 3.4 K.</p> </abstract>