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 language | English |
|---|---|
| Pages (from-to) | 969-977 |
| Number of pages | 9 |
| Journal | Inorganic Chemistry |
| Volume | 21 |
| Issue number | 3 |
| Publication status | Published - 1982 |
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- Inorganic Chemistry
Cite this
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.; Marks, Tobin J.
In: Inorganic Chemistry, Vol. 21, No. 3, 1982, p. 969-977.Research output: Contribution to journal › Article
}
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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M3 - Article
VL - 21
SP - 969
EP - 977
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 3
ER -