Syntheses and Crystal Structures of CsCuNd2Se4 and CsCuGd2Te4: Two Non-Isotypical Cesium Copper Lanthanide Chalcogenides with 1∞{[CuCh3]5-} Chains of Vertex-Shared [CuCh4]7- Tetrahedra

被引:18
作者
Babo, Jean-Marie [1 ]
Strobel, Sabine [1 ]
Schleid, Thomas [1 ]
机构
[1] Univ Stuttgart, Inst Anorgan Chem, D-70569 Stuttgart, Germany
来源
ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE | 2010年 / 636卷 / 02期
关键词
Lanthanides; Cesium; Copper; Chalcogenides; Tunnel structures; PHYSICAL-PROPERTIES; LN; SELENIDES; ND; GD; SM;
D O I
10.1002/zaac.200900419
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The new chalcogenides CsCuNd2Se4 and CsCuGd2Te4 with analogous formulae were prepared front the elements by a flux method with CsCl as fluxing agent and cesium source. CsCuNd2Se4 crystalline in the othorhombic space group Cmcm (n0. 63) with four formula units per unit cell (a = 424.69(3), b = 1475.81 (8), c = 1465.42(8) pm) whereas CsCuGd2Te4 is monoclinic with the space group C2/m (no. 12) and twelve formula units per unit cell (a = 3764.75(19), b = 436.70(2), c = 2105.37(11) pm, beta = 107.423(4)degrees). Both crystal structures feature three-dimensional arrangements of the lanthanide and coinage metal cations along with the chalcogenide anions according to (3)(infinity){[CuLn(2)Ch(4)](-)} (Ln = Nd or Gd, Ch = Se or Te), leaving channels behind, in which the Cs+ cations are incorporated. Hereby, vertex-linked [CuCh(4)](7-) tetrahedra join to form (1)(infinity){[CuCh(3)](5-)} chains in both cases. Whereas for the CsCuNd2Se4 structure, these chains ((1)(infinity){[CuSe3](5-)}) are embedded into a three-dimensional network, erected by edge- and vertex-linked [NdSe6](9) octahedra, which form corrugated layers further connected by common edges, in CsCuGd2Te4 a different three-dimensional (3)(infinity){[Gd2Te4](2)} framework arises, comprising (1)(infinity){[CuTe3](5-)} chains, as well as vertex- and edge-linked [GdTe6](9-) octahedra. The major difference of the structures originates from the channels, in which the Cs+ cations are located. In the tunnels of CsCuNd2Se4, the Cs+ cations exhibit a bicapped trigonal prismatic selenide coordination, whereas in CsCuGd2Tc4 with two Cs+ cations in one channel, they show bicapped trigonal prisms, as well as monocapped cubes of telluride anions as coordination spheres.
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页码:349 / 355
页数:7
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