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Structure of Jahn-Teller distorted solvated copper(II) ions in solution, and in solids with apparently regular octahedral coordination geometry

Persson, I.; Persson, Per LU ; Sandstrom, M. and Ullstrom, A. S. (2002) In Journal of the Chemical Society. Dalton Transactions p.1256-1265
Abstract
Regular octahedral coordination has been reported for some copper(II) complexes in the solid state on the basis of crystallographic studies, e.g. hexaaquacopper(II) bromate, [Cu(OH2)(6)](BrO3)(2). hexaaquacopper(II) hexafluorosilicate, [Cu(OH2)(6)]Si-6, and hexakis(pyridine-1-oxide)copper(II) perchlorate. [Cu(ONC5H5)(6)](ClO4)(2). These results are not consistent with the elongated octahedral configuration expected from the Jahn-Teller theorem for the d(9) copper(II) ion nor, in some cases, with results from electron spin resonance studies. The present lattice-independent EXAFS study confirms that the local structure in the copper(II) complexes mentioned above is, in all cases, consistent with a Jahn-Teller induced elongation. Mean... (More)
Regular octahedral coordination has been reported for some copper(II) complexes in the solid state on the basis of crystallographic studies, e.g. hexaaquacopper(II) bromate, [Cu(OH2)(6)](BrO3)(2). hexaaquacopper(II) hexafluorosilicate, [Cu(OH2)(6)]Si-6, and hexakis(pyridine-1-oxide)copper(II) perchlorate. [Cu(ONC5H5)(6)](ClO4)(2). These results are not consistent with the elongated octahedral configuration expected from the Jahn-Teller theorem for the d(9) copper(II) ion nor, in some cases, with results from electron spin resonance studies. The present lattice-independent EXAFS study confirms that the local structure in the copper(II) complexes mentioned above is, in all cases, consistent with a Jahn-Teller induced elongation. Mean equatorial and axial Cu-O bond distances of 1.96(1) and 2.32(2) Angstrom, and 1.95(1) and 2.27(3) Angstrom, were obtained for the hexaaquacopper(II) ions in the bromate and hexafluorosilicate salts, respectively, For the hexakis(pyridine-1-oxide)copper(II) perchlorate only the equatorial mean Cu 0 bond distance of 1.96(1) Angstrom could be observed. Evidently, there is orientational disorder of the tetragonally elongated octahedral complexes resulting in too high crystallographic space group symmetry and copper sites in apparently regular coordination geometry. For the hydrated copper(II) ion in aqueous solution, five- and six-coordinated models with different geometries have been evaluated by means of EXAFS and large angle X-ray diffraction (LAXS) data. The combined results are consistent with a Jahn-Teller elongated octahedral configuration with Cu-O-eq 1.95(1) Angstrom, Cu-O-ax 2.29(3) Angstrom, and a distinct second hydration sphere with about eight water molecules and a mean Cu...O-II distance of 4.17(3) Angstrom. In dimethylsulfoxide solution EXAFS and LAXS methods show the solvated copper(II) ions to have mean equatorial and axial Cu-O bond distances of 1.96(1) and 2.24(2) Angstrom, respectively, As a model compound for the EXAFS studies, the crystal structure of hexakis(dimethylsulfoxide)copper(II) perchlorate dimethylsulfoxide (1/2), [Cu(OS(CH3)(2))(6)](ClO4)(2).2(CH3)(2)SO, was determined. (Less)
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author
publishing date
type
Contribution to journal
publication status
published
subject
in
Journal of the Chemical Society. Dalton Transactions
issue
7
pages
1256 - 1265
publisher
Royal Society of Chemistry
external identifiers
  • scopus:0036010403
ISSN
1472-7773
DOI
10.1039/B200698G
language
English
LU publication?
no
id
df63693f-057c-488c-aa7b-43da9f0cd9c5 (old id 4332570)
date added to LUP
2014-03-04 09:42:56
date last changed
2017-11-12 03:55:50
@article{df63693f-057c-488c-aa7b-43da9f0cd9c5,
  abstract     = {Regular octahedral coordination has been reported for some copper(II) complexes in the solid state on the basis of crystallographic studies, e.g. hexaaquacopper(II) bromate, [Cu(OH2)(6)](BrO3)(2). hexaaquacopper(II) hexafluorosilicate, [Cu(OH2)(6)]Si-6, and hexakis(pyridine-1-oxide)copper(II) perchlorate. [Cu(ONC5H5)(6)](ClO4)(2). These results are not consistent with the elongated octahedral configuration expected from the Jahn-Teller theorem for the d(9) copper(II) ion nor, in some cases, with results from electron spin resonance studies. The present lattice-independent EXAFS study confirms that the local structure in the copper(II) complexes mentioned above is, in all cases, consistent with a Jahn-Teller induced elongation. Mean equatorial and axial Cu-O bond distances of 1.96(1) and 2.32(2) Angstrom, and 1.95(1) and 2.27(3) Angstrom, were obtained for the hexaaquacopper(II) ions in the bromate and hexafluorosilicate salts, respectively, For the hexakis(pyridine-1-oxide)copper(II) perchlorate only the equatorial mean Cu 0 bond distance of 1.96(1) Angstrom could be observed. Evidently, there is orientational disorder of the tetragonally elongated octahedral complexes resulting in too high crystallographic space group symmetry and copper sites in apparently regular coordination geometry. For the hydrated copper(II) ion in aqueous solution, five- and six-coordinated models with different geometries have been evaluated by means of EXAFS and large angle X-ray diffraction (LAXS) data. The combined results are consistent with a Jahn-Teller elongated octahedral configuration with Cu-O-eq 1.95(1) Angstrom, Cu-O-ax 2.29(3) Angstrom, and a distinct second hydration sphere with about eight water molecules and a mean Cu...O-II distance of 4.17(3) Angstrom. In dimethylsulfoxide solution EXAFS and LAXS methods show the solvated copper(II) ions to have mean equatorial and axial Cu-O bond distances of 1.96(1) and 2.24(2) Angstrom, respectively, As a model compound for the EXAFS studies, the crystal structure of hexakis(dimethylsulfoxide)copper(II) perchlorate dimethylsulfoxide (1/2), [Cu(OS(CH3)(2))(6)](ClO4)(2).2(CH3)(2)SO, was determined.},
  author       = {Persson, I. and Persson, Per and Sandstrom, M. and Ullstrom, A. S.},
  issn         = {1472-7773},
  language     = {eng},
  number       = {7},
  pages        = {1256--1265},
  publisher    = {Royal Society of Chemistry},
  series       = {Journal of the Chemical Society. Dalton Transactions},
  title        = {Structure of Jahn-Teller distorted solvated copper(II) ions in solution, and in solids with apparently regular octahedral coordination geometry},
  url          = {http://dx.doi.org/10.1039/B200698G},
  year         = {2002},
}