Metal ion binding sites composed of multiple nitrogenous heterocycles. Synthesis and spectral and structural study of bis(2,2′,2″-tripyridylamine)copper(II) bis(trifluoromethanesulfonate) and its bis(acetonitrile) adduct

Patricia L. Dedert, Jeffery S. Thompson, James A. Ibers, Tobin J Marks

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Abstract

The copper complex [Cu(N(py)3)2(CH3CN)2][SO 3CF3]2, N(py)3 = 2,2′,2″-tripyridylamine, can be prepared by the reaction of Cu(SO3CF3)2 with N(py)3 in acetonitrile. The complex Cu(N(py)3)2(SO3CF3)2 can be prepared from Cu(SO3CF3)2 and N(py)3 in methanol or by recrystallizing the bis(acetonitrile) complex from acetone/ether. The bis(acetonitrile) complex crystallizes in the monoclinic space group C2h 5-P21/n with two molecules in a unit cell of dimensions a = 11.825 (2) Å, b = 14.774 (3) Å, c = 11.516 (2) Å, and β = 97.699 (4)°. Least-squares refinement of the 193 variables led to a value of the conventional R index (on F) of 0.070 for 1669 reflections having Fo 2 > 3σ(Fo 2). The geometry about the cupric ion is tetragonally distorted octahedral (crystallographically imposed symmetry 1) with two pyridyl rings from each bidentate N(py)3 ligand defining the equatorial coordination. The Cu(II) ion and four nitrogen atoms are rigorously coplanar, with an average Cu-N distance of 2.020 (3) Å. The acetonitrile ligands occupy axial ligation positions with a Cu-N distance of 2.526 (8) Å. The above complexes have been studied by infrared, optical, and EPR spectroscopy. The vibrational spectroscopic results in the N(py)3 and SO3CF3 skeletal regions are in accord with bidentate N(py)3 coordination in both compounds. For Cu(N(py)3)2(SO3CF3)2, axial triflate coordination is indicated. The optical and EPR spectral data are also in accord with these structural conclusions. For [Cu(N(py)3)2(CH3CN)2][SO 3CF3]2, the 14N superhyperfine coupling shows the pyridyl and acetonitrile donors to be magnetically indistinguishable.

Original languageEnglish
Pages (from-to)969-977
Number of pages9
JournalInorganic Chemistry
Volume21
Issue number3
Publication statusPublished - 1982

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adducts
acetonitrile
Metal ions
Copper
metal ions
Binding Sites
copper
synthesis
Paramagnetic resonance
Ions
Ligands
ligands
Acetone
Ether
nitrogen atoms
spectroscopy
acetone
Methanol
ethers
ions

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

@article{463585fa55f44f9b80c5e7df8e7e39b1,
title = "Metal ion binding sites composed of multiple nitrogenous heterocycles. Synthesis and spectral and structural study of bis(2,2′,2″-tripyridylamine)copper(II) bis(trifluoromethanesulfonate) and its bis(acetonitrile) adduct",
abstract = "The copper complex [Cu(N(py)3)2(CH3CN)2][SO 3CF3]2, N(py)3 = 2,2′,2″-tripyridylamine, can be prepared by the reaction of Cu(SO3CF3)2 with N(py)3 in acetonitrile. The complex Cu(N(py)3)2(SO3CF3)2 can be prepared from Cu(SO3CF3)2 and N(py)3 in methanol or by recrystallizing the bis(acetonitrile) complex from acetone/ether. The bis(acetonitrile) complex crystallizes in the monoclinic space group C2h 5-P21/n with two molecules in a unit cell of dimensions a = 11.825 (2) {\AA}, b = 14.774 (3) {\AA}, c = 11.516 (2) {\AA}, and β = 97.699 (4)°. Least-squares refinement of the 193 variables led to a value of the conventional R index (on F) of 0.070 for 1669 reflections having Fo 2 > 3σ(Fo 2). The geometry about the cupric ion is tetragonally distorted octahedral (crystallographically imposed symmetry 1) with two pyridyl rings from each bidentate N(py)3 ligand defining the equatorial coordination. The Cu(II) ion and four nitrogen atoms are rigorously coplanar, with an average Cu-N distance of 2.020 (3) {\AA}. The acetonitrile ligands occupy axial ligation positions with a Cu-N distance of 2.526 (8) {\AA}. The above complexes have been studied by infrared, optical, and EPR spectroscopy. The vibrational spectroscopic results in the N(py)3 and SO3CF3 skeletal regions are in accord with bidentate N(py)3 coordination in both compounds. For Cu(N(py)3)2(SO3CF3)2, axial triflate coordination is indicated. The optical and EPR spectral data are also in accord with these structural conclusions. For [Cu(N(py)3)2(CH3CN)2][SO 3CF3]2, the 14N superhyperfine coupling shows the pyridyl and acetonitrile donors to be magnetically indistinguishable.",
author = "Dedert, {Patricia L.} and Thompson, {Jeffery S.} and Ibers, {James A.} and Marks, {Tobin J}",
year = "1982",
language = "English",
volume = "21",
pages = "969--977",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "3",

}

TY - JOUR

T1 - Metal ion binding sites composed of multiple nitrogenous heterocycles. Synthesis and spectral and structural study of bis(2,2′,2″-tripyridylamine)copper(II) bis(trifluoromethanesulfonate) and its bis(acetonitrile) adduct

AU - Dedert, Patricia L.

AU - Thompson, Jeffery S.

AU - Ibers, James A.

AU - Marks, Tobin J

PY - 1982

Y1 - 1982

N2 - The copper complex [Cu(N(py)3)2(CH3CN)2][SO 3CF3]2, N(py)3 = 2,2′,2″-tripyridylamine, can be prepared by the reaction of Cu(SO3CF3)2 with N(py)3 in acetonitrile. The complex Cu(N(py)3)2(SO3CF3)2 can be prepared from Cu(SO3CF3)2 and N(py)3 in methanol or by recrystallizing the bis(acetonitrile) complex from acetone/ether. The bis(acetonitrile) complex crystallizes in the monoclinic space group C2h 5-P21/n with two molecules in a unit cell of dimensions a = 11.825 (2) Å, b = 14.774 (3) Å, c = 11.516 (2) Å, and β = 97.699 (4)°. Least-squares refinement of the 193 variables led to a value of the conventional R index (on F) of 0.070 for 1669 reflections having Fo 2 > 3σ(Fo 2). The geometry about the cupric ion is tetragonally distorted octahedral (crystallographically imposed symmetry 1) with two pyridyl rings from each bidentate N(py)3 ligand defining the equatorial coordination. The Cu(II) ion and four nitrogen atoms are rigorously coplanar, with an average Cu-N distance of 2.020 (3) Å. The acetonitrile ligands occupy axial ligation positions with a Cu-N distance of 2.526 (8) Å. The above complexes have been studied by infrared, optical, and EPR spectroscopy. The vibrational spectroscopic results in the N(py)3 and SO3CF3 skeletal regions are in accord with bidentate N(py)3 coordination in both compounds. For Cu(N(py)3)2(SO3CF3)2, axial triflate coordination is indicated. The optical and EPR spectral data are also in accord with these structural conclusions. For [Cu(N(py)3)2(CH3CN)2][SO 3CF3]2, the 14N superhyperfine coupling shows the pyridyl and acetonitrile donors to be magnetically indistinguishable.

AB - The copper complex [Cu(N(py)3)2(CH3CN)2][SO 3CF3]2, N(py)3 = 2,2′,2″-tripyridylamine, can be prepared by the reaction of Cu(SO3CF3)2 with N(py)3 in acetonitrile. The complex Cu(N(py)3)2(SO3CF3)2 can be prepared from Cu(SO3CF3)2 and N(py)3 in methanol or by recrystallizing the bis(acetonitrile) complex from acetone/ether. The bis(acetonitrile) complex crystallizes in the monoclinic space group C2h 5-P21/n with two molecules in a unit cell of dimensions a = 11.825 (2) Å, b = 14.774 (3) Å, c = 11.516 (2) Å, and β = 97.699 (4)°. Least-squares refinement of the 193 variables led to a value of the conventional R index (on F) of 0.070 for 1669 reflections having Fo 2 > 3σ(Fo 2). The geometry about the cupric ion is tetragonally distorted octahedral (crystallographically imposed symmetry 1) with two pyridyl rings from each bidentate N(py)3 ligand defining the equatorial coordination. The Cu(II) ion and four nitrogen atoms are rigorously coplanar, with an average Cu-N distance of 2.020 (3) Å. The acetonitrile ligands occupy axial ligation positions with a Cu-N distance of 2.526 (8) Å. The above complexes have been studied by infrared, optical, and EPR spectroscopy. The vibrational spectroscopic results in the N(py)3 and SO3CF3 skeletal regions are in accord with bidentate N(py)3 coordination in both compounds. For Cu(N(py)3)2(SO3CF3)2, axial triflate coordination is indicated. The optical and EPR spectral data are also in accord with these structural conclusions. For [Cu(N(py)3)2(CH3CN)2][SO 3CF3]2, the 14N superhyperfine coupling shows the pyridyl and acetonitrile donors to be magnetically indistinguishable.

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