Two Hexagonal Series of Lanthanoid(III) Oxide Fluoride Selenides: M6O2F8Se3 (M = La – Nd) and M2OF2Se (M = Nd, Sm, Gd – Ho)

Zeitschrift fur Anorganische und Allgemeine Chemie - Tập 641 Số 11 - Trang 1926-1933 - 2015
Dirk D. Zimmermann1, Hagen Grossholz1, Sarah Wolf1, Oliver Janka1,2, Alexander Müller1,3, Thomas Schleid1
1Institut für Anorganische Chemie, Universität Stuttgart, Pfaffenwaldring 55, 70569 Stuttgart, Germany
2Institut für Anorganische und Analytische Chemie, Westfälische Wilhelms-Universität Münster, Corrensstraße 28/30, 48149 Münster, Germany
3Institut für Textilchemie und Chemiefasern, Körschtalstr. 26, 73770 Denkendorf, Germany

Tóm tắt

Abstract

Two hexagonal series of lanthanoid(III) oxide fluoride selenides with similar structure types can be obtained by the reaction of the components MF3, M2O3, M, and Se in sealed niobium tubes at 850 °C using CsI as fluxing agent. The compounds with the lighter and larger representatives (M = La – Nd) occur with the formula M6O2F8Se3, whereas with the heavier and smaller ones (M = Nd, Sm, Gd – Ho) their composition is M2OF2Se. For both systems single‐crystal determinations were used in all cases. The compounds crystallize in the hexagonal crystal system (space group: P63/m) with lattice parameters of a = 1394–1331 pm and c = 403–372 pm (Z = 2 for M6O2F8Se3 and Z = 6 for M2OF2Se). The (M1)3+ cations show different square antiprismatic coordination spheres with or without an extra capping fluoride anion. All (M2)3+ cations exhibit a ninefold coordination environment shaped as tricapped trigonal prism. In both structure types the Se2– anions are sixfold coordinated as trigonal prisms of M3+ cations, being first condensed by edges to generate trimeric units and then via faces to form strands running along [001]. The light anions reside either in threefold triangular or in fourfold tetrahedral cationic coordination. For charge compensation, both structures have to contain a certain amount of oxide besides fluoride anions. Since F– and O2– can not be distinguished by X‐ray diffraction, bond‐valence calculations were used to address the problem of their adjunction to the available crystallographic sites.

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Zeitschrift fur Anorganische und Allgemeine Chemie

Tập 641 Số 11

1926-1933

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