Cation-anion interactions and polar structures in the solid state

Michael R. Marvel; Julien Lesage; Jaewook Baek; P. Shiv Halasyamani; Charlotte L. Stern; Kenneth R. Poeppelmeier

doi:10.1021/ja074659h

Cation-anion interactions and polar structures in the solid state

Michael R. Marvel, Julien Lesage, Jaewook Baek, P. Shiv Halasyamani, Charlotte L. Stern, Kenneth R. Poeppelmeier^*

^*Corresponding author for this work

Chemistry

Research output: Contribution to journal › Article › peer-review

171 Scopus citations

Abstract

Complicated structures where oxygen and fluorine are found together in one framework, where deviations from Pauling's second crystal rule (PSCR) are expected, often result in structures with important physical properties. The [NbOF₅]^2- anion and therefore all the individual Nb-O and Nb-F bonds are ordered in noncentrosymmetric KNaNbOF₅ and centrosymmetric CsNaNbOF₅. The Na/K- and Na/Cs-O/F interactions in these phases, in particular the expected deviations from PSCR and the bond valence model, reveal the essential role of the small potassium cations in the acentric packing of the [NbOF₅]^2- anion. KNaNbOF ₅ crystallizes in the orthorhombic and polar space group Pna2 ₁ (No. 33) with lattice constants a = 11.8653(11) Å, b = 5.8826(6) Å, c = 8.1258(8) Å, and Z = 4, while CsNaNbOF₅ crystallizes in the orthorhombic space group Pbcn (No. 60) with lattice constants a = 8.3155(7), b = 13.3176(11), c = 11.1314-(9), and Z = 8.

Original language	English (US)
Pages (from-to)	13963-13969
Number of pages	7
Journal	Journal of the American Chemical Society
Volume	129
Issue number	45
DOIs	https://doi.org/10.1021/ja074659h
State	Published - Nov 14 2007

ASJC Scopus subject areas

Catalysis
Chemistry(all)
Biochemistry
Colloid and Surface Chemistry

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title = "Cation-anion interactions and polar structures in the solid state",

abstract = "Complicated structures where oxygen and fluorine are found together in one framework, where deviations from Pauling's second crystal rule (PSCR) are expected, often result in structures with important physical properties. The [NbOF5]2- anion and therefore all the individual Nb-O and Nb-F bonds are ordered in noncentrosymmetric KNaNbOF5 and centrosymmetric CsNaNbOF5. The Na/K- and Na/Cs-O/F interactions in these phases, in particular the expected deviations from PSCR and the bond valence model, reveal the essential role of the small potassium cations in the acentric packing of the [NbOF5]2- anion. KNaNbOF 5 crystallizes in the orthorhombic and polar space group Pna2 1 (No. 33) with lattice constants a = 11.8653(11) {\AA}, b = 5.8826(6) {\AA}, c = 8.1258(8) {\AA}, and Z = 4, while CsNaNbOF5 crystallizes in the orthorhombic space group Pbcn (No. 60) with lattice constants a = 8.3155(7), b = 13.3176(11), c = 11.1314-(9), and Z = 8.",

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AU - Marvel, Michael R.

AU - Lesage, Julien

AU - Baek, Jaewook

AU - Halasyamani, P. Shiv

AU - Stern, Charlotte L.

AU - Poeppelmeier, Kenneth R.

PY - 2007/11/14

Y1 - 2007/11/14

N2 - Complicated structures where oxygen and fluorine are found together in one framework, where deviations from Pauling's second crystal rule (PSCR) are expected, often result in structures with important physical properties. The [NbOF5]2- anion and therefore all the individual Nb-O and Nb-F bonds are ordered in noncentrosymmetric KNaNbOF5 and centrosymmetric CsNaNbOF5. The Na/K- and Na/Cs-O/F interactions in these phases, in particular the expected deviations from PSCR and the bond valence model, reveal the essential role of the small potassium cations in the acentric packing of the [NbOF5]2- anion. KNaNbOF 5 crystallizes in the orthorhombic and polar space group Pna2 1 (No. 33) with lattice constants a = 11.8653(11) Å, b = 5.8826(6) Å, c = 8.1258(8) Å, and Z = 4, while CsNaNbOF5 crystallizes in the orthorhombic space group Pbcn (No. 60) with lattice constants a = 8.3155(7), b = 13.3176(11), c = 11.1314-(9), and Z = 8.

AB - Complicated structures where oxygen and fluorine are found together in one framework, where deviations from Pauling's second crystal rule (PSCR) are expected, often result in structures with important physical properties. The [NbOF5]2- anion and therefore all the individual Nb-O and Nb-F bonds are ordered in noncentrosymmetric KNaNbOF5 and centrosymmetric CsNaNbOF5. The Na/K- and Na/Cs-O/F interactions in these phases, in particular the expected deviations from PSCR and the bond valence model, reveal the essential role of the small potassium cations in the acentric packing of the [NbOF5]2- anion. KNaNbOF 5 crystallizes in the orthorhombic and polar space group Pna2 1 (No. 33) with lattice constants a = 11.8653(11) Å, b = 5.8826(6) Å, c = 8.1258(8) Å, and Z = 4, while CsNaNbOF5 crystallizes in the orthorhombic space group Pbcn (No. 60) with lattice constants a = 8.3155(7), b = 13.3176(11), c = 11.1314-(9), and Z = 8.

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Cation-anion interactions and polar structures in the solid state

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