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

doi:10.1021/ic00133a020

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

^*Corresponding author for this work

Chemistry

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Abstract

The copper complex [Cu(N(py)₃)₂(CH₃CN)₂][SO₃CF₃]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 C_2h⁵-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 F_o² > 3σ(F_o²). The geometry about the cupric ion is tetragonally distorted octahedral (crystallographically imposed symmetry 1̄) 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][SO₃CF₃]₂, the ¹⁴N superhyperfine coupling shows the pyridyl and acetonitrile donors to be magnetically indistinguishable.

Original language	English (US)
Pages (from-to)	969-977
Number of pages	9
Journal	Inorganic chemistry
Volume	21
Issue number	3
DOIs	https://doi.org/10.1021/ic00133a020
State	Published - 1982

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Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{79a16c427ebe462e8940165aa5de2654,

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][SO3CF3]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 C2h5-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 Fo2 > 3σ(Fo2). 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][SO3CF3]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",

doi = "10.1021/ic00133a020",

language = "English (US)",

volume = "21",

pages = "969--977",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "3",

}

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. / Dedert, Patricia L.; Thompson, Jeffery S.; Ibers, James A. et al.

In: Inorganic chemistry, Vol. 21, No. 3, 1982, p. 969-977.

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

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][SO3CF3]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 C2h5-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 Fo2 > 3σ(Fo2). The geometry about the cupric ion is tetragonally distorted octahedral (crystallographically imposed symmetry 1̄) 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][SO3CF3]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][SO3CF3]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 C2h5-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 Fo2 > 3σ(Fo2). The geometry about the cupric ion is tetragonally distorted octahedral (crystallographically imposed symmetry 1̄) 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][SO3CF3]2, the 14N superhyperfine coupling shows the pyridyl and acetonitrile donors to be magnetically indistinguishable.

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UR - http://www.scopus.com/inward/citedby.url?scp=0001089978&partnerID=8YFLogxK

U2 - 10.1021/ic00133a020

DO - 10.1021/ic00133a020

M3 - Article

AN - SCOPUS:0001089978

SN - 0020-1669

VL - 21

SP - 969

EP - 977

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 3

ER -

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

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