Tetrahedral coordination for Zn in hexacyanometallates: Structures of Zn<inf>3</inf>A<inf>2</inf>[M(CN)<inf>6</inf>]<inf>2</inf>·xH<inf>2</inf>O with A=K, Rb, Cs and M=Ru, Os

M. Avila, L. Reguera, C. Vargas, E. Reguera

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Abstract

Zinc hexacyanoruthenate (II) and hexacyanoosmate (II) were prepared and studied from X-ray diffraction (XRD), infrared (IR), and thermogravimetric (TG) data. These compounds were found to be isomorphous with the iron analogues, crystallizing with a rhombohedral unit cell (R-3c space group), where the zinc atom has tetrahedral coordination to N ends of CN groups. For Cs, compounds with formula unit ZnCs2[M(CN)6] and a cubic unit cell (Fm-3m) were also obtained. The crystal structures for the eight compositions were refined from the corresponding X-ray powder diffraction patterns using the Rietveld method. Related to the tetrahedral coordination for the Zn atom, the rhombohedral phase has a porous framework with ellipsoidal cavities of about 12.5×9×8 Å, communicated by elliptical windows of ∼5 Å. Within these cavities the exchangeable alkali metal ions are found. The filling of the cavity volume is completed with water molecules. IR spectrum senses certain charge delocalization from the inner metal, through the π-back donation mechanism. For Os compounds this effect is particularly pronounced, related to a more diffuse d orbitals for this metal. © 2008 Elsevier Ltd. All rights reserved.
Original languageAmerican English
Pages (from-to)477-482
Number of pages428
JournalJournal of Physics and Chemistry of Solids
DOIs
StatePublished - 1 Jan 2009

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Zinc
Metals
Alkali Metals
Infrared radiation
Rietveld method
Atoms
cavities
Alkali metals
zinc
X ray powder diffraction
Diffraction patterns
Metal ions
Iron
Crystal structure
cells
X ray diffraction
metals
alkali metals
Molecules
atoms

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@article{01e53f72350e420d8fef4a458497521f,
title = "Tetrahedral coordination for Zn in hexacyanometallates: Structures of Zn3A2[M(CN)6]2·xH2O with A=K, Rb, Cs and M=Ru, Os",
abstract = "Zinc hexacyanoruthenate (II) and hexacyanoosmate (II) were prepared and studied from X-ray diffraction (XRD), infrared (IR), and thermogravimetric (TG) data. These compounds were found to be isomorphous with the iron analogues, crystallizing with a rhombohedral unit cell (R-3c space group), where the zinc atom has tetrahedral coordination to N ends of CN groups. For Cs, compounds with formula unit ZnCs2[M(CN)6] and a cubic unit cell (Fm-3m) were also obtained. The crystal structures for the eight compositions were refined from the corresponding X-ray powder diffraction patterns using the Rietveld method. Related to the tetrahedral coordination for the Zn atom, the rhombohedral phase has a porous framework with ellipsoidal cavities of about 12.5×9×8 {\AA}, communicated by elliptical windows of ∼5 {\AA}. Within these cavities the exchangeable alkali metal ions are found. The filling of the cavity volume is completed with water molecules. IR spectrum senses certain charge delocalization from the inner metal, through the π-back donation mechanism. For Os compounds this effect is particularly pronounced, related to a more diffuse d orbitals for this metal. {\circledC} 2008 Elsevier Ltd. All rights reserved.",
author = "M. Avila and L. Reguera and C. Vargas and E. Reguera",
year = "2009",
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language = "American English",
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T1 - Tetrahedral coordination for Zn in hexacyanometallates: Structures of Zn3A2[M(CN)6]2·xH2O with A=K, Rb, Cs and M=Ru, Os

AU - Avila, M.

AU - Reguera, L.

AU - Vargas, C.

AU - Reguera, E.

PY - 2009/1/1

Y1 - 2009/1/1

N2 - Zinc hexacyanoruthenate (II) and hexacyanoosmate (II) were prepared and studied from X-ray diffraction (XRD), infrared (IR), and thermogravimetric (TG) data. These compounds were found to be isomorphous with the iron analogues, crystallizing with a rhombohedral unit cell (R-3c space group), where the zinc atom has tetrahedral coordination to N ends of CN groups. For Cs, compounds with formula unit ZnCs2[M(CN)6] and a cubic unit cell (Fm-3m) were also obtained. The crystal structures for the eight compositions were refined from the corresponding X-ray powder diffraction patterns using the Rietveld method. Related to the tetrahedral coordination for the Zn atom, the rhombohedral phase has a porous framework with ellipsoidal cavities of about 12.5×9×8 Å, communicated by elliptical windows of ∼5 Å. Within these cavities the exchangeable alkali metal ions are found. The filling of the cavity volume is completed with water molecules. IR spectrum senses certain charge delocalization from the inner metal, through the π-back donation mechanism. For Os compounds this effect is particularly pronounced, related to a more diffuse d orbitals for this metal. © 2008 Elsevier Ltd. All rights reserved.

AB - Zinc hexacyanoruthenate (II) and hexacyanoosmate (II) were prepared and studied from X-ray diffraction (XRD), infrared (IR), and thermogravimetric (TG) data. These compounds were found to be isomorphous with the iron analogues, crystallizing with a rhombohedral unit cell (R-3c space group), where the zinc atom has tetrahedral coordination to N ends of CN groups. For Cs, compounds with formula unit ZnCs2[M(CN)6] and a cubic unit cell (Fm-3m) were also obtained. The crystal structures for the eight compositions were refined from the corresponding X-ray powder diffraction patterns using the Rietveld method. Related to the tetrahedral coordination for the Zn atom, the rhombohedral phase has a porous framework with ellipsoidal cavities of about 12.5×9×8 Å, communicated by elliptical windows of ∼5 Å. Within these cavities the exchangeable alkali metal ions are found. The filling of the cavity volume is completed with water molecules. IR spectrum senses certain charge delocalization from the inner metal, through the π-back donation mechanism. For Os compounds this effect is particularly pronounced, related to a more diffuse d orbitals for this metal. © 2008 Elsevier Ltd. All rights reserved.

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