Synthesis, Crystal Structure and Properties of the New Laminar Quaternary Tellurides Sr Ln CuTe 3 (Ln = Sm, Gd–Tm and Lu).

Autor: Ruseikina, Anna V., Grigoriev, Maxim V., Molokeev, Maxim S., Garmonov, Alexander A., Elyshev, Andrey V., Locke, Ralf J. C., Schleid, Thomas
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Zdroj: Crystals (2073-4352); Feb2023, Vol. 13 Issue 2, p291, 16p
Abstrakt: This paper reports for the first time on the new laminar quaternary orthorhombic heterometallic quaternary tellurides SrLnCuTe3, the fabrication of which has been a challenge until this work. Data on the crystal structure of tellurides complete the series of quaternary strontium chalcogenides SrLnCuCh3 (Ch = S, Se, Te). Single crystals of the compounds were synthesized from the elements by the halogenide-flux method at 1070 K. The compounds are crystallizing in two space groups Pnma (Ln = Sm, Gd and Tb) and Cmcm (Ln = Dy–Tm and Lu). For SrSmCuTe3 (a = 11.4592(7), b = 4.3706(3), c = 14.4425(9) Å, space group: Pnma) with the largest lanthanoid cation, Sr2+ shows C.N. = 7, whereas Sm3+ reveals a diminished coordination number C.N. = 6. For SrLuCuTe3 (a = 4.3064(3), b = 14.3879(9), c = 11.1408(7) Å, space group: Cmcm) with the smallest lanthanoid cation, coordination numbers of six are realized for both high-charged cations (Sr2+ and Lu3+: C.N. = 6). The cations Sr2+, Ln3+, Cu+ each take independent positions. The structures are built by distorted [CuTe4]7– tetrahedra, forming the infinite chains { ∞ 1 [ Cu (Te 1) 1 / 1 t (Te 2) 1 / 1 t (Te 3) 2 / 2 e ] 5 − } along [010] in SrLnCuTe3 (Ln = Sm, Gd and Tb) and [100] in SrLnCuTe3 (Ln = Dy–Tm and Lu). The distortion of the polyhedra [CuTe4]7– was compared for the whole series SrLnCuTe3 by means of τ4-descriptor for the four coordinating Te2– anions, which revealed a decrease in the degree of distortion with a decreasing radius at Ln3+. The distorted octahedra [LnTe6]9– form layers { ∞ 2 [ L n (Te 1) 2 / 2 (Te 2) 2 / 2 (Te 3) 2 / 2 ] 3 − } . The distorted octahedra and tetrahedra fuse to form parallel layers { ∞ 2 [ Cu L n Te 3 ] 2 − } and between them, the Sr2+ cations providing three-dimensionality of the structure are located. In the SrLnCuTe3 (Ln = Sm, Gd and Tb) structures, the Sr2+ cations center capped the trigonal prisms [SrTe6+1]12−, united in infinite chains { ∞ 1 [ Sr (Te 1) 2 / 2 (Te 2) 3 / 3 (Te 3) 2 / 2 ] 4 − } along the [100] direction. The domains of existence of the Ba2MnS3, BaLaCuS3, Eu2CuS3 and KZrCuS3 structure types are defined in the series of orthorhombic chalcogenides SrLnCuCh3 (Ch = S, Se and Te). The tellurides SrLnCuTe3 (Ln = Tb–Er) of both structure types in the temperature range from 2 up to 300 K are paramagnetic, without showing clear signs of a magnetic phase transition. [ABSTRACT FROM AUTHOR]
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