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Sulfidisch derivatisierte Oxodisilicate der schweren Lanthanide vom Formeltyp M4S3[Si2O7] (M = Gd - Tm) / Sulfide Derivatized Oxodisilicates of the Heavy Lanthanides with the Formula M4S3[Si2O7] (M = Gd - Tm)
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Corinna Sieke
Published/Copyright:
June 2, 2014
The sulfide derivatized oxodisilicates M4S3[Si2O7] of the heavy lanthanides (M = Gd - Tm) have been synthesized by reaction of M, M2O3, S, and SiO2 using MCl3 as flux in evacuated silica tubes at 850 °C for 7 d. The title compounds crystallize tetragonally in the space group I41/amd with 8 formula units per unit cell. Their crystal structure contains isolated [Si2O7]6− pyroanions of two vertex-sharing [SiO4] tetrahedra in eclipsed conformation with Si-O-Si bridging angles of about 130°. The two crystallographically independent lanthanide cations (M3+) both reside in tricapped trigonal prismatic environments of chalcogen ligands. In the case of M1 five S2− and three plus one O2− anions (CN = 8+1), for M2 three S2− and six O2− anions (CN = 9) fill the coordination spheres. Two of the three different sulfide anions are surrounded by four M3+ cations forming a seesaw (S2) and a square (S3), respectively. The third one (S1) is coordinated by six lanthanide cations in the form of a distorted octahedron. The whole structure is basically built up of cationic lanthanide silicate layers which are threaded by sulfide anions.
Received: 2002-8-29
Published Online: 2014-6-2
Published in Print: 2002-12-1
© 1946 – 2014: Verlag der Zeitschrift für Naturforschung
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