Examining the out-of-center distortion in the [NbOF5] 2- anion

Heather K. Izumi, Janet E. Kirsch, Charlotte L. Stern, Kenneth R Poeppelmeier

Research output: Contribution to journalArticle

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Abstract

Out-of-center "primary" electronic distortions are inherent to the oxide fluoride anions of the early d0 transition metals. In the [NbOF5]2- anion, the Nb5+ moves from the center of the octahedron toward the oxide ligand to form a short Nb=O bond and long trans Nb-F bond. The combined results of single-crystal X-ray diffraction and electronic structure calculations indicate that the primary distortion of the [NbOF5]2- anion is affected by the coordination environment that is created by the three-dimensional extended structure. The formation of bonds between an M(L)42+ (M = Cd 2+, Cu2+; L = 3-aminopyridine, 4-aminopyridine) cation and the oxide and/or trans-fluoride ligands of the [NbOF5]2- anion weakens the π component of the Nb=O bond. At the same time, hydrogen bond interactions between the equatorial fluorides and the aminopyridine groups both lengthen the equatorial Nb-F bonds and can further reduce the symmetry of the [NbOF5]2- anion. These combined three-dimensional bond network interactions that serve to lengthen the Nb=O bond and thereby decrease the primary distortion of the [NbOF5]2- anion are illustrated in the structures of three new niobium oxide fluoride phases, [4-apyH]2[Cu(4-apy)4(NbOF5)2] (4-apy = 4-aminopyridine), Cd(3-apy)4NbOF5 (3-apy = 3-aminopyridine), and Cu(3-apy)4NbOF5, that were synthesized and characterized using X-ray diffraction. Crystal data for [4-apyH]2[Cu(4-apy)4(NbOF5)2]: tetragonal, space group /41/ acd (No. 142), with a = 20.8745(8) Å, c = 17.2929(9) Å, and Z = 8. Cd(3-apy)4NbOF 5: tetragonal, space group P43 (No. 78), with a = 8.4034(4) Å, c = 34.933(3) Å, and Z = 4. Cu(3-apy) 4NbOF5: monoclinic, space group P21/n (No. 14), with a = 8.822(1) Å, b = 16.385(3) Å, c = 8.902(1) Å, β = 109.270(3)°, and Z = 2.

Original languageEnglish
Pages (from-to)884-895
Number of pages12
JournalInorganic Chemistry
Volume44
Issue number4
DOIs
Publication statusPublished - Feb 21 2005

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Anions
anions
Fluorides
fluorides
Oxides
4-Aminopyridine
oxides
Aminopyridines
Niobium oxide
Ligands
niobium oxides
X ray diffraction
ligands
diffraction
Electronic structure
Transition metals
Cations
Hydrogen bonds
x rays
transition metals

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Examining the out-of-center distortion in the [NbOF5] 2- anion. / Izumi, Heather K.; Kirsch, Janet E.; Stern, Charlotte L.; Poeppelmeier, Kenneth R.

In: Inorganic Chemistry, Vol. 44, No. 4, 21.02.2005, p. 884-895.

Research output: Contribution to journalArticle

Izumi, Heather K. ; Kirsch, Janet E. ; Stern, Charlotte L. ; Poeppelmeier, Kenneth R. / Examining the out-of-center distortion in the [NbOF5] 2- anion. In: Inorganic Chemistry. 2005 ; Vol. 44, No. 4. pp. 884-895.
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abstract = "Out-of-center {"}primary{"} electronic distortions are inherent to the oxide fluoride anions of the early d0 transition metals. In the [NbOF5]2- anion, the Nb5+ moves from the center of the octahedron toward the oxide ligand to form a short Nb=O bond and long trans Nb-F bond. The combined results of single-crystal X-ray diffraction and electronic structure calculations indicate that the primary distortion of the [NbOF5]2- anion is affected by the coordination environment that is created by the three-dimensional extended structure. The formation of bonds between an M(L)42+ (M = Cd 2+, Cu2+; L = 3-aminopyridine, 4-aminopyridine) cation and the oxide and/or trans-fluoride ligands of the [NbOF5]2- anion weakens the π component of the Nb=O bond. At the same time, hydrogen bond interactions between the equatorial fluorides and the aminopyridine groups both lengthen the equatorial Nb-F bonds and can further reduce the symmetry of the [NbOF5]2- anion. These combined three-dimensional bond network interactions that serve to lengthen the Nb=O bond and thereby decrease the primary distortion of the [NbOF5]2- anion are illustrated in the structures of three new niobium oxide fluoride phases, [4-apyH]2[Cu(4-apy)4(NbOF5)2] (4-apy = 4-aminopyridine), Cd(3-apy)4NbOF5 (3-apy = 3-aminopyridine), and Cu(3-apy)4NbOF5, that were synthesized and characterized using X-ray diffraction. Crystal data for [4-apyH]2[Cu(4-apy)4(NbOF5)2]: tetragonal, space group /41/ acd (No. 142), with a = 20.8745(8) {\AA}, c = 17.2929(9) {\AA}, and Z = 8. Cd(3-apy)4NbOF 5: tetragonal, space group P43 (No. 78), with a = 8.4034(4) {\AA}, c = 34.933(3) {\AA}, and Z = 4. Cu(3-apy) 4NbOF5: monoclinic, space group P21/n (No. 14), with a = 8.822(1) {\AA}, b = 16.385(3) {\AA}, c = 8.902(1) {\AA}, β = 109.270(3)°, and Z = 2.",
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T1 - Examining the out-of-center distortion in the [NbOF5] 2- anion

AU - Izumi, Heather K.

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N2 - Out-of-center "primary" electronic distortions are inherent to the oxide fluoride anions of the early d0 transition metals. In the [NbOF5]2- anion, the Nb5+ moves from the center of the octahedron toward the oxide ligand to form a short Nb=O bond and long trans Nb-F bond. The combined results of single-crystal X-ray diffraction and electronic structure calculations indicate that the primary distortion of the [NbOF5]2- anion is affected by the coordination environment that is created by the three-dimensional extended structure. The formation of bonds between an M(L)42+ (M = Cd 2+, Cu2+; L = 3-aminopyridine, 4-aminopyridine) cation and the oxide and/or trans-fluoride ligands of the [NbOF5]2- anion weakens the π component of the Nb=O bond. At the same time, hydrogen bond interactions between the equatorial fluorides and the aminopyridine groups both lengthen the equatorial Nb-F bonds and can further reduce the symmetry of the [NbOF5]2- anion. These combined three-dimensional bond network interactions that serve to lengthen the Nb=O bond and thereby decrease the primary distortion of the [NbOF5]2- anion are illustrated in the structures of three new niobium oxide fluoride phases, [4-apyH]2[Cu(4-apy)4(NbOF5)2] (4-apy = 4-aminopyridine), Cd(3-apy)4NbOF5 (3-apy = 3-aminopyridine), and Cu(3-apy)4NbOF5, that were synthesized and characterized using X-ray diffraction. Crystal data for [4-apyH]2[Cu(4-apy)4(NbOF5)2]: tetragonal, space group /41/ acd (No. 142), with a = 20.8745(8) Å, c = 17.2929(9) Å, and Z = 8. Cd(3-apy)4NbOF 5: tetragonal, space group P43 (No. 78), with a = 8.4034(4) Å, c = 34.933(3) Å, and Z = 4. Cu(3-apy) 4NbOF5: monoclinic, space group P21/n (No. 14), with a = 8.822(1) Å, b = 16.385(3) Å, c = 8.902(1) Å, β = 109.270(3)°, and Z = 2.

AB - Out-of-center "primary" electronic distortions are inherent to the oxide fluoride anions of the early d0 transition metals. In the [NbOF5]2- anion, the Nb5+ moves from the center of the octahedron toward the oxide ligand to form a short Nb=O bond and long trans Nb-F bond. The combined results of single-crystal X-ray diffraction and electronic structure calculations indicate that the primary distortion of the [NbOF5]2- anion is affected by the coordination environment that is created by the three-dimensional extended structure. The formation of bonds between an M(L)42+ (M = Cd 2+, Cu2+; L = 3-aminopyridine, 4-aminopyridine) cation and the oxide and/or trans-fluoride ligands of the [NbOF5]2- anion weakens the π component of the Nb=O bond. At the same time, hydrogen bond interactions between the equatorial fluorides and the aminopyridine groups both lengthen the equatorial Nb-F bonds and can further reduce the symmetry of the [NbOF5]2- anion. These combined three-dimensional bond network interactions that serve to lengthen the Nb=O bond and thereby decrease the primary distortion of the [NbOF5]2- anion are illustrated in the structures of three new niobium oxide fluoride phases, [4-apyH]2[Cu(4-apy)4(NbOF5)2] (4-apy = 4-aminopyridine), Cd(3-apy)4NbOF5 (3-apy = 3-aminopyridine), and Cu(3-apy)4NbOF5, that were synthesized and characterized using X-ray diffraction. Crystal data for [4-apyH]2[Cu(4-apy)4(NbOF5)2]: tetragonal, space group /41/ acd (No. 142), with a = 20.8745(8) Å, c = 17.2929(9) Å, and Z = 8. Cd(3-apy)4NbOF 5: tetragonal, space group P43 (No. 78), with a = 8.4034(4) Å, c = 34.933(3) Å, and Z = 4. Cu(3-apy) 4NbOF5: monoclinic, space group P21/n (No. 14), with a = 8.822(1) Å, b = 16.385(3) Å, c = 8.902(1) Å, β = 109.270(3)°, and Z = 2.

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