[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

doi:10.1021/ic970951m

[pyH]₂[Cu(py)₄(MX₆)₂] (MX₆ = ZrF₆^2- , NbOF₅^2- , MoO₂F₄^2- ; 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^*

^*Corresponding author for this work

Chemistry

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Abstract

Single crystals of [pyH]₂[Cu(py)₄(MX₆)₂] (MX₆ = ZrF₆^2-, MoO₂F₄^2-; 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 NbOF₅^2- and MoO₂F₄^2- 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 language	English (US)
Pages (from-to)	76-80
Number of pages	5
Journal	Inorganic chemistry
Volume	37
Issue number	1
DOIs	https://doi.org/10.1021/ic970951m
State	Published - Jan 12 1998

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{f57bcd1631b9412e95f798e11e99f9d7,

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.",

author = "Heier, {Kevin R.} and Norquist, {Alexander J.} and Wilson, {Christopher G.} and Stern, {Charlotte L.} and Poeppelmeier, {Kenneth R.}",

year = "1998",

month = jan,

day = "12",

doi = "10.1021/ic970951m",

language = "English (US)",

volume = "37",

pages = "76--80",

journal = "Inorganic chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "1",

}

TY - JOUR

T1 - [pyH]2[Cu(py)4(MX6)2] (MX6 = ZrF62- , NbOF52- , MoO2F42- ; py = Pyridine)

T2 - Rarely Observed Ordering of Metal Oxide Fiuoride Anions

AU - Heier, Kevin R.

AU - Norquist, Alexander J.

AU - Wilson, Christopher G.

AU - Stern, Charlotte L.

AU - Poeppelmeier, Kenneth R.

PY - 1998/1/12

Y1 - 1998/1/12

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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[pyH]₂[Cu(py)₄(MX₆)₂] (MX₆ = ZrF₆^2- , NbOF₅^2- , MoO₂F₄^2- ; py = Pyridine): Rarely Observed Ordering of Metal Oxide Fiuoride Anions

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