[pyH]2[Cu(py)4(MX6)2] (MX6 = ZrF62- , NbOF52- , MoO2F42- ; py = Pyridine): Rarely Observed Ordering of Metal Oxide Fiuoride Anions

Kevin R. Heier, Alexander J. Norquist, Christopher G. Wilson, Charlotte L. Stern, Kenneth R Poeppelmeier

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Abstract

Single crystals of [pyH]2[Cu(py)4(MX6)2] (MX6 = ZrF62-, MoO2F42-; py = pyridine), analogous to those of the previously reported [pyH]2[Cu(py)4(NbOF5)2], were synthesized by reaction of the metal oxides in (HF)x·pyridine/ pyridine/water solutions (150 °C, autogeneous pressure). The NbOF52- and MoO2F42- anions generally crystallize with orientational disorder masking the true coordination geometry. The combination of the two different and strongly coordinating cations tetrakis(pyridine)copper(II) and pyridinium causes the anions to adopt regular and ordered orientations. Crystal data: for [pyH]2[Cu(py)4(ZrF6)2], tetragonal, space group I4/mmm (No. 139), with a = 11.047(1) Å, c = 16.763(3) Å, and Z = 2; for [pyH]2[Cu(py)4(MoO2F4):]. monoclinic, space group C2/c (No. 15), with a = 19.195(4) Å, b = 11.316(3) Å, c = 18.920(5) Å, β= 107.68(2)°, and Z = 4.

Original languageEnglish
Pages (from-to)76-80
Number of pages5
JournalInorganic Chemistry
Volume37
Issue number1
Publication statusPublished - Jan 12 1998

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Oxides
Anions
metal oxides
pyridines
Metals
anions
masking
Crystal orientation
Cations
Copper
Single crystals
disorders
cations
copper
Crystals
Geometry
Water
causes
single crystals
geometry

ASJC Scopus subject areas

  • Inorganic Chemistry

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[pyH]2[Cu(py)4(MX6)2] (MX6 = ZrF62- , NbOF52- , MoO2F42- ; py = Pyridine) : Rarely Observed Ordering of Metal Oxide Fiuoride Anions. / Heier, Kevin R.; Norquist, Alexander J.; Wilson, Christopher G.; Stern, Charlotte L.; Poeppelmeier, Kenneth R.

In: Inorganic Chemistry, Vol. 37, No. 1, 12.01.1998, p. 76-80.

Research output: Contribution to journalArticle

Heier, Kevin R. ; Norquist, Alexander J. ; Wilson, Christopher G. ; Stern, Charlotte L. ; Poeppelmeier, Kenneth R. / [pyH]2[Cu(py)4(MX6)2] (MX6 = ZrF62- , NbOF52- , MoO2F42- ; py = Pyridine) : Rarely Observed Ordering of Metal Oxide Fiuoride Anions. In: Inorganic Chemistry. 1998 ; Vol. 37, No. 1. pp. 76-80.
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title = "[pyH]2[Cu(py)4(MX6)2] (MX6 = ZrF62- , NbOF52- , MoO2F42- ; py = Pyridine): Rarely Observed Ordering of Metal Oxide Fiuoride Anions",
abstract = "Single crystals of [pyH]2[Cu(py)4(MX6)2] (MX6 = ZrF62-, MoO2F42-; py = pyridine), analogous to those of the previously reported [pyH]2[Cu(py)4(NbOF5)2], were synthesized by reaction of the metal oxides in (HF)x·pyridine/ pyridine/water solutions (150 °C, autogeneous pressure). The NbOF52- and MoO2F42- anions generally crystallize with orientational disorder masking the true coordination geometry. The combination of the two different and strongly coordinating cations tetrakis(pyridine)copper(II) and pyridinium causes the anions to adopt regular and ordered orientations. Crystal data: for [pyH]2[Cu(py)4(ZrF6)2], tetragonal, space group I4/mmm (No. 139), with a = 11.047(1) {\AA}, c = 16.763(3) {\AA}, and Z = 2; for [pyH]2[Cu(py)4(MoO2F4):]. monoclinic, space group C2/c (No. 15), with a = 19.195(4) {\AA}, b = 11.316(3) {\AA}, c = 18.920(5) {\AA}, β= 107.68(2)°, and Z = 4.",
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AU - Heier, Kevin R.

AU - Norquist, Alexander J.

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AU - Poeppelmeier, Kenneth R

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N2 - Single crystals of [pyH]2[Cu(py)4(MX6)2] (MX6 = ZrF62-, MoO2F42-; py = pyridine), analogous to those of the previously reported [pyH]2[Cu(py)4(NbOF5)2], were synthesized by reaction of the metal oxides in (HF)x·pyridine/ pyridine/water solutions (150 °C, autogeneous pressure). The NbOF52- and MoO2F42- anions generally crystallize with orientational disorder masking the true coordination geometry. The combination of the two different and strongly coordinating cations tetrakis(pyridine)copper(II) and pyridinium causes the anions to adopt regular and ordered orientations. Crystal data: for [pyH]2[Cu(py)4(ZrF6)2], tetragonal, space group I4/mmm (No. 139), with a = 11.047(1) Å, c = 16.763(3) Å, and Z = 2; for [pyH]2[Cu(py)4(MoO2F4):]. monoclinic, space group C2/c (No. 15), with a = 19.195(4) Å, b = 11.316(3) Å, c = 18.920(5) Å, β= 107.68(2)°, and Z = 4.

AB - Single crystals of [pyH]2[Cu(py)4(MX6)2] (MX6 = ZrF62-, MoO2F42-; py = pyridine), analogous to those of the previously reported [pyH]2[Cu(py)4(NbOF5)2], were synthesized by reaction of the metal oxides in (HF)x·pyridine/ pyridine/water solutions (150 °C, autogeneous pressure). The NbOF52- and MoO2F42- anions generally crystallize with orientational disorder masking the true coordination geometry. The combination of the two different and strongly coordinating cations tetrakis(pyridine)copper(II) and pyridinium causes the anions to adopt regular and ordered orientations. Crystal data: for [pyH]2[Cu(py)4(ZrF6)2], tetragonal, space group I4/mmm (No. 139), with a = 11.047(1) Å, c = 16.763(3) Å, and Z = 2; for [pyH]2[Cu(py)4(MoO2F4):]. monoclinic, space group C2/c (No. 15), with a = 19.195(4) Å, b = 11.316(3) Å, c = 18.920(5) Å, β= 107.68(2)°, and Z = 4.

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