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Title: The lanthanoid(III) chloride cyclo-tetrasilicates M{sub 6}Cl{sub 10}[Si{sub 4}O{sub 12}] (M=Sm, Gd-Dy): Synthesis, structure and IR investigations

Abstract

The chloride derivatized lanthanoid(III) cyclo-tetrasilicates of the composition M{sub 6}Cl{sub 10}[Si{sub 4}O{sub 12}] (M=Sm, Gd-Dy) crystallize monoclinically in space group C2/m (a=1062-1065, b=1036-1052, c=1163-1187pm, {beta}{approx}103{sup o}, Z=2). They are obtained by the reaction of the sesquioxides M{sub 2}O{sub 3} (or the combination of Tb{sub 4}O{sub 7} and Tb in 3:2-molar ratio for the terbium case), the corresponding trichlorides MCl{sub 3}, and SiO{sub 2} (silica gel) in stoichiometric ratios with double the amount of MCl{sub 3} as flux in evacuated silica tubes (7d at 850deg. C) as transparent, pseudo-octagonal, pillar-shaped single crystals with the colour of the respective lanthanoid trication M{sup 3+}. Their crystal structure can be considered as a layered arrangement in which cationic {sub {approx}}{sup 2}{l_brace}[(M2){sub 5}Cl{sub 9}]{sup 6+}{r_brace} layers are alternatingly piled with anionic ones of the kind {sub {approx}}{sup 2}{l_brace}[(M1)Cl[Si{sub 4}O{sub 12}]]{sup 6-}{r_brace}. In the latter, the (M1){sup 3+} cations show a slightly distorted hexagonal bipyramidal environment built up by two Cl{sup -} and six O{sup 2-} anions (CN=8), whereas the (M2){sup 3+} cations exhibit a coordination number of only seven (five Cl{sup -} and two O{sup 2-} anions in the shape of a distorted pentagonal bipyramid). The cyclo-tetrasilicate units consist of four corner-linked [SiO{sub 4}]{sup 4-}more » tetrahedra in all-ecliptical conformation each, fused to eight-membered rings, which contain two almost linear (178{sup o}) and two bent (142{sup o}) Si-O-Si bridges. This particular cyclo-[Si{sub 4}O{sub 12}]{sup 8-} situation could be confirmed by theoretical and experimental infrared-spectroscopic investigations.« less

Authors:
 [1];  [2];  [1]
  1. Institute for Inorganic Chemistry, University of Stuttgart, D-70569 Stuttgart (Germany)
  2. Institute for Physical Chemistry, University of Stuttgart, D-70569 Stuttgart (Germany)
Publication Date:
OSTI Identifier:
20905374
Resource Type:
Journal Article
Journal Name:
Journal of Solid State Chemistry
Additional Journal Information:
Journal Volume: 179; Journal Issue: 8; Other Information: DOI: 10.1016/j.jssc.2006.01.063; PII: S0022-4596(06)00072-7; Copyright (c) 2006 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA); Journal ID: ISSN 0022-4596
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; CHLORINE IONS; DYSPROSIUM CHLORIDES; GADOLINIUM CHLORIDES; INFRARED SPECTRA; MONOCLINIC LATTICES; MONOCRYSTALS; OXYGEN IONS; SAMARIUM CHLORIDES; SILICA; SILICA GEL; SILICATES; SILICON OXIDES; SPACE GROUPS; STOICHIOMETRY; SYNTHESIS; TERBIUM CHLORIDES; TERBIUM OXIDES

Citation Formats

Hartenbach, Ingo, Jagiella, Stefan, and Schleid, Thomas. The lanthanoid(III) chloride cyclo-tetrasilicates M{sub 6}Cl{sub 10}[Si{sub 4}O{sub 12}] (M=Sm, Gd-Dy): Synthesis, structure and IR investigations. United States: N. p., 2006. Web. doi:10.1016/j.jssc.2006.01.063.
Hartenbach, Ingo, Jagiella, Stefan, & Schleid, Thomas. The lanthanoid(III) chloride cyclo-tetrasilicates M{sub 6}Cl{sub 10}[Si{sub 4}O{sub 12}] (M=Sm, Gd-Dy): Synthesis, structure and IR investigations. United States. https://doi.org/10.1016/j.jssc.2006.01.063
Hartenbach, Ingo, Jagiella, Stefan, and Schleid, Thomas. 2006. "The lanthanoid(III) chloride cyclo-tetrasilicates M{sub 6}Cl{sub 10}[Si{sub 4}O{sub 12}] (M=Sm, Gd-Dy): Synthesis, structure and IR investigations". United States. https://doi.org/10.1016/j.jssc.2006.01.063.
@article{osti_20905374,
title = {The lanthanoid(III) chloride cyclo-tetrasilicates M{sub 6}Cl{sub 10}[Si{sub 4}O{sub 12}] (M=Sm, Gd-Dy): Synthesis, structure and IR investigations},
author = {Hartenbach, Ingo and Jagiella, Stefan and Schleid, Thomas},
abstractNote = {The chloride derivatized lanthanoid(III) cyclo-tetrasilicates of the composition M{sub 6}Cl{sub 10}[Si{sub 4}O{sub 12}] (M=Sm, Gd-Dy) crystallize monoclinically in space group C2/m (a=1062-1065, b=1036-1052, c=1163-1187pm, {beta}{approx}103{sup o}, Z=2). They are obtained by the reaction of the sesquioxides M{sub 2}O{sub 3} (or the combination of Tb{sub 4}O{sub 7} and Tb in 3:2-molar ratio for the terbium case), the corresponding trichlorides MCl{sub 3}, and SiO{sub 2} (silica gel) in stoichiometric ratios with double the amount of MCl{sub 3} as flux in evacuated silica tubes (7d at 850deg. C) as transparent, pseudo-octagonal, pillar-shaped single crystals with the colour of the respective lanthanoid trication M{sup 3+}. Their crystal structure can be considered as a layered arrangement in which cationic {sub {approx}}{sup 2}{l_brace}[(M2){sub 5}Cl{sub 9}]{sup 6+}{r_brace} layers are alternatingly piled with anionic ones of the kind {sub {approx}}{sup 2}{l_brace}[(M1)Cl[Si{sub 4}O{sub 12}]]{sup 6-}{r_brace}. In the latter, the (M1){sup 3+} cations show a slightly distorted hexagonal bipyramidal environment built up by two Cl{sup -} and six O{sup 2-} anions (CN=8), whereas the (M2){sup 3+} cations exhibit a coordination number of only seven (five Cl{sup -} and two O{sup 2-} anions in the shape of a distorted pentagonal bipyramid). The cyclo-tetrasilicate units consist of four corner-linked [SiO{sub 4}]{sup 4-} tetrahedra in all-ecliptical conformation each, fused to eight-membered rings, which contain two almost linear (178{sup o}) and two bent (142{sup o}) Si-O-Si bridges. This particular cyclo-[Si{sub 4}O{sub 12}]{sup 8-} situation could be confirmed by theoretical and experimental infrared-spectroscopic investigations.},
doi = {10.1016/j.jssc.2006.01.063},
url = {https://www.osti.gov/biblio/20905374}, journal = {Journal of Solid State Chemistry},
issn = {0022-4596},
number = 8,
volume = 179,
place = {United States},
year = {Tue Aug 15 00:00:00 EDT 2006},
month = {Tue Aug 15 00:00:00 EDT 2006}
}