Synthesis and crystal structures of gallium and germanium variants of cancrinite

Yongjae Lee, John B. Parise, Akhilesh Tripathi, Sun Jin Kim, Thomas Vogt

Research output: Contribution to journalArticle

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Abstract

A synthetic alummogermanate and a gallogermanate with the Cancrinite group (CAN) framework topology have been synthesized under hydrothermal conditions and characterized by single crystal synchrotron X-ray diffraction. AlGe-CAN, Na6Cs2Al6Ge6O24·Ge(OH)6, is hexagonal, with the space group P63 and a = 12.968(1), c = 5.132(1) angstroms, V = 747.4(1) angstroms3. The T-sites exhibit complete ordering of Al and Ge atoms, similar to the framework models of aluminosilicate analogues. GaGe-CAN, Na6Cs2Ga6Ge6O24·Ge(OH)6, is hexagonal, apparently with the space group P63mc and a = 12.950(2), c = 5.117(1) angstroms, V = 743.2(2) angstroms3. Although the observed data are consistent with the presence of the c-glide and consequent disordering of Ga and Ge atoms at the T-sites, calculation using a DLS-optimized framework in the space group P63 reveals that the intensities of the hh2̄h̄l reflections with l = 2n+1 are less than 0.07% of the strongest (0 0 0 2) reflection, suggesting that P63 is probably the true space group. Resonant diffraction studies performed in the vicinity of the Ga K-edge confirmed the presence of the hh2̄h̄l reflections with l = 2n+1 and thus confirmed the ordering of the framework Ga/Ge atoms in GaGe-CAN. Inspection of the framework T-O-T bond angles demonstrates greater relative cell contraction for GaGe-CAN compared to AlGe-CAN and aluminosilicate counterparts. In both the structural models, Ge(OH)6 octahedra are occluded in the 12-ring channels running along the 63-axes. The sodium cations fully occupy the sites above the 6-ring windows in the 12-ring channels. The cesium cations fully occupy the sites in the middle of the cancrinite cages. Subtle differences in the coordination geometries of the extra-framework species are found, perhaps due to the pseudo-symmetry of GaGe-CAN. Thermogravimetry results indicate net weight losses of 3.5% and 3.0% for AlGe-CAN and GaGe-CAN, respectively, which are explainable by the dehydration of the Ge(OH)6 octahedra. In situ synchrotron X-ray powder diffraction demonstrated the formation of GaGe analogue of the nepheline hydrate I type structure at the temperature of complete dehydration.

Original languageEnglish
Pages (from-to)445-455
Number of pages11
JournalMicroporous and Mesoporous Materials
Volume39
Issue number3
DOIs
Publication statusPublished - 2000 Jan 1

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Germanium
Gallium
Gages
gallium
germanium
Crystal structure
crystal structure
synthesis
Aluminosilicates
Synchrotrons
Dehydration
Atoms
Cations
Positive ions
Cesium
Hydrates
X ray powder diffraction
dehydration
Thermogravimetric analysis
rings

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics
  • Mechanics of Materials

Cite this

Lee, Yongjae ; Parise, John B. ; Tripathi, Akhilesh ; Kim, Sun Jin ; Vogt, Thomas. / Synthesis and crystal structures of gallium and germanium variants of cancrinite. In: Microporous and Mesoporous Materials. 2000 ; Vol. 39, No. 3. pp. 445-455.
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title = "Synthesis and crystal structures of gallium and germanium variants of cancrinite",
abstract = "A synthetic alummogermanate and a gallogermanate with the Cancrinite group (CAN) framework topology have been synthesized under hydrothermal conditions and characterized by single crystal synchrotron X-ray diffraction. AlGe-CAN, Na6Cs2Al6Ge6O24·Ge(OH)6, is hexagonal, with the space group P63 and a = 12.968(1), c = 5.132(1) angstroms, V = 747.4(1) angstroms3. The T-sites exhibit complete ordering of Al and Ge atoms, similar to the framework models of aluminosilicate analogues. GaGe-CAN, Na6Cs2Ga6Ge6O24·Ge(OH)6, is hexagonal, apparently with the space group P63mc and a = 12.950(2), c = 5.117(1) angstroms, V = 743.2(2) angstroms3. Although the observed data are consistent with the presence of the c-glide and consequent disordering of Ga and Ge atoms at the T-sites, calculation using a DLS-optimized framework in the space group P63 reveals that the intensities of the hh2̄h̄l reflections with l = 2n+1 are less than 0.07{\%} of the strongest (0 0 0 2) reflection, suggesting that P63 is probably the true space group. Resonant diffraction studies performed in the vicinity of the Ga K-edge confirmed the presence of the hh2̄h̄l reflections with l = 2n+1 and thus confirmed the ordering of the framework Ga/Ge atoms in GaGe-CAN. Inspection of the framework T-O-T bond angles demonstrates greater relative cell contraction for GaGe-CAN compared to AlGe-CAN and aluminosilicate counterparts. In both the structural models, Ge(OH)6 octahedra are occluded in the 12-ring channels running along the 63-axes. The sodium cations fully occupy the sites above the 6-ring windows in the 12-ring channels. The cesium cations fully occupy the sites in the middle of the cancrinite cages. Subtle differences in the coordination geometries of the extra-framework species are found, perhaps due to the pseudo-symmetry of GaGe-CAN. Thermogravimetry results indicate net weight losses of 3.5{\%} and 3.0{\%} for AlGe-CAN and GaGe-CAN, respectively, which are explainable by the dehydration of the Ge(OH)6 octahedra. In situ synchrotron X-ray powder diffraction demonstrated the formation of GaGe analogue of the nepheline hydrate I type structure at the temperature of complete dehydration.",
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Synthesis and crystal structures of gallium and germanium variants of cancrinite. / Lee, Yongjae; Parise, John B.; Tripathi, Akhilesh; Kim, Sun Jin; Vogt, Thomas.

In: Microporous and Mesoporous Materials, Vol. 39, No. 3, 01.01.2000, p. 445-455.

Research output: Contribution to journalArticle

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T1 - Synthesis and crystal structures of gallium and germanium variants of cancrinite

AU - Lee, Yongjae

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N2 - A synthetic alummogermanate and a gallogermanate with the Cancrinite group (CAN) framework topology have been synthesized under hydrothermal conditions and characterized by single crystal synchrotron X-ray diffraction. AlGe-CAN, Na6Cs2Al6Ge6O24·Ge(OH)6, is hexagonal, with the space group P63 and a = 12.968(1), c = 5.132(1) angstroms, V = 747.4(1) angstroms3. The T-sites exhibit complete ordering of Al and Ge atoms, similar to the framework models of aluminosilicate analogues. GaGe-CAN, Na6Cs2Ga6Ge6O24·Ge(OH)6, is hexagonal, apparently with the space group P63mc and a = 12.950(2), c = 5.117(1) angstroms, V = 743.2(2) angstroms3. Although the observed data are consistent with the presence of the c-glide and consequent disordering of Ga and Ge atoms at the T-sites, calculation using a DLS-optimized framework in the space group P63 reveals that the intensities of the hh2̄h̄l reflections with l = 2n+1 are less than 0.07% of the strongest (0 0 0 2) reflection, suggesting that P63 is probably the true space group. Resonant diffraction studies performed in the vicinity of the Ga K-edge confirmed the presence of the hh2̄h̄l reflections with l = 2n+1 and thus confirmed the ordering of the framework Ga/Ge atoms in GaGe-CAN. Inspection of the framework T-O-T bond angles demonstrates greater relative cell contraction for GaGe-CAN compared to AlGe-CAN and aluminosilicate counterparts. In both the structural models, Ge(OH)6 octahedra are occluded in the 12-ring channels running along the 63-axes. The sodium cations fully occupy the sites above the 6-ring windows in the 12-ring channels. The cesium cations fully occupy the sites in the middle of the cancrinite cages. Subtle differences in the coordination geometries of the extra-framework species are found, perhaps due to the pseudo-symmetry of GaGe-CAN. Thermogravimetry results indicate net weight losses of 3.5% and 3.0% for AlGe-CAN and GaGe-CAN, respectively, which are explainable by the dehydration of the Ge(OH)6 octahedra. In situ synchrotron X-ray powder diffraction demonstrated the formation of GaGe analogue of the nepheline hydrate I type structure at the temperature of complete dehydration.

AB - A synthetic alummogermanate and a gallogermanate with the Cancrinite group (CAN) framework topology have been synthesized under hydrothermal conditions and characterized by single crystal synchrotron X-ray diffraction. AlGe-CAN, Na6Cs2Al6Ge6O24·Ge(OH)6, is hexagonal, with the space group P63 and a = 12.968(1), c = 5.132(1) angstroms, V = 747.4(1) angstroms3. The T-sites exhibit complete ordering of Al and Ge atoms, similar to the framework models of aluminosilicate analogues. GaGe-CAN, Na6Cs2Ga6Ge6O24·Ge(OH)6, is hexagonal, apparently with the space group P63mc and a = 12.950(2), c = 5.117(1) angstroms, V = 743.2(2) angstroms3. Although the observed data are consistent with the presence of the c-glide and consequent disordering of Ga and Ge atoms at the T-sites, calculation using a DLS-optimized framework in the space group P63 reveals that the intensities of the hh2̄h̄l reflections with l = 2n+1 are less than 0.07% of the strongest (0 0 0 2) reflection, suggesting that P63 is probably the true space group. Resonant diffraction studies performed in the vicinity of the Ga K-edge confirmed the presence of the hh2̄h̄l reflections with l = 2n+1 and thus confirmed the ordering of the framework Ga/Ge atoms in GaGe-CAN. Inspection of the framework T-O-T bond angles demonstrates greater relative cell contraction for GaGe-CAN compared to AlGe-CAN and aluminosilicate counterparts. In both the structural models, Ge(OH)6 octahedra are occluded in the 12-ring channels running along the 63-axes. The sodium cations fully occupy the sites above the 6-ring windows in the 12-ring channels. The cesium cations fully occupy the sites in the middle of the cancrinite cages. Subtle differences in the coordination geometries of the extra-framework species are found, perhaps due to the pseudo-symmetry of GaGe-CAN. Thermogravimetry results indicate net weight losses of 3.5% and 3.0% for AlGe-CAN and GaGe-CAN, respectively, which are explainable by the dehydration of the Ge(OH)6 octahedra. In situ synchrotron X-ray powder diffraction demonstrated the formation of GaGe analogue of the nepheline hydrate I type structure at the temperature of complete dehydration.

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