Syntheses, crystal structures and spectroscopic properties of KEu[AsS4], K3Dy[AsS4](2) and Rb4Nd0.67[AsS4](2).

Wu, Y. D. and Bensch, Wolfgang (2009) Syntheses, crystal structures and spectroscopic properties of KEu[AsS4], K3Dy[AsS4](2) and Rb4Nd0.67[AsS4](2). Solid State Sciences, 11 (9). pp. 1542-1548. DOI 10.1016/j.solidstatesciences.2009.06.027.

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Supplementary data:

Abstract

Three rare earth compounds, KEu[AsS4] (1), K3Dy[AsS4](2) (2), and Rb4Nd0.67[AsS4](2) (3) have been synthesized employing the molten flux method. The reactions of A(2)S(3) (A = K, Rb), Ln (Ln = Eu, Dy, Nd), As2S3, S were accomplished at 600 degrees C for 96 h in evacuated fused silica ampoules. Crystal data for these compounds are: 1, monoclinic, space group P2(1)/m (no. 11), a = 6.7276(7) angstrom, b = 6.7190(5) angstrom, c = 8.6947(9) angstrom, 107.287(12)degrees, Z = 2; 2, monoclinic, space group C2/c (no. 15), a = 10.3381(7) angstrom, b = 18.7439(12) angstrom, c = 8.8185(6) angstrom, beta = 117.060(7)degrees, Z = 4; 3, orthorhombic, space group Ibam (no. 72), a = 18.7333(15) angstrom, b = 9.1461(5) angstrom, c = 10.2060(6) angstrom, Z = 4. 1 is a two-dimensional structure with (2)(infinity)[Eu(AsS4)](-) layers separated by potassium cations. Within each layer, distorted bicapped trigonal [EuS8] prisms are linked through distorted [AsS4](3-) tetrahedra. Each Eu2+ cation is coordinated by two [AsS4](3-) units by edge-sharing and bonded to further two [AsS4](3-) units by corner-sharing. Compound 2 contains a one-dimensional structure with (1)(infinity)[Dy(AsS4)(2)](3-) chains separated by potassium cations. Within each chain, distorted bicapped trigonal prisms of [DyS8] are linked by slightly distorted [AsS4](3-) tetrahedra. Each Dy3+ ion is surrounded by four [AsS4](3-) moieties in an edge-sharing fashion. For compound 3 also a one-dimensional structure with (1)(infinity)[Nd-0.67(AsS4)(2)](4-) chains is observed. But the Nd position is only partially occupied and overall every third Nd atom is missing along the chain. This cuts the infinite chains into short dimers containing two bridging [As-4](3-) units and four terminal [AsS4](3-) groups. 1 is characterized with UV/vis diffuse reflectance spectroscopy, IR, and Raman spectra. (C) 2009 Elsevier Masson SAS. All rights reserved.

Document Type: Article
Keywords: rare earththioarsenates; crystal structure; spectroscopic properties; thioarsenate compounds; thiophosphate; chains; chalcogenides; conjunction; keupse4; fluxes; gd; ln;
Research affiliation: OceanRep > The Future Ocean - Cluster of Excellence
Kiel University
Refereed: Yes
Open Access Journal?: No
Publisher: Elsevier
Projects: Future Ocean
Date Deposited: 16 Nov 2010 09:39
Last Modified: 28 Jul 2019 06:02
URI: https://oceanrep.geomar.de/id/eprint/9851

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