Influence of lattice interactions on the Jahn-Teller distortion of the [Cu(H2O)6]2+ ion: dependence of the crystal structure of K2xRb2-2x[Cu(H2O)6](SeO4)2 upon the K/Rb ratio

Simmons, Charles J., Stratemeier, Horst, Hitchman, Michael A. and Riley, Mark J. (2013) Influence of lattice interactions on the Jahn-Teller distortion of the [Cu(H2O)6]2+ ion: dependence of the crystal structure of K2xRb2-2x[Cu(H2O)6](SeO4)2 upon the K/Rb ratio. Inorganic Chemistry, 52 18: 10481-10499. doi:10.1021/ic401385f


Author Simmons, Charles J.
Stratemeier, Horst
Hitchman, Michael A.
Riley, Mark J.
Title Influence of lattice interactions on the Jahn-Teller distortion of the [Cu(H2O)6]2+ ion: dependence of the crystal structure of K2xRb2-2x[Cu(H2O)6](SeO4)2 upon the K/Rb ratio
Formatted title
Influence of lattice interactions on the Jahn–Teller distortion of the [Cu(H2O)6]2+ ion: dependence of the crystal structure of K2xRb2-2x[Cu(H2O)6](SeO4)2 upon the K/Rb ratio
Journal name Inorganic Chemistry   Check publisher's open access policy
ISSN 0020-1669
1520-510X
Publication date 2013-09-16
Sub-type Article (original research)
DOI 10.1021/ic401385f
Open Access Status
Volume 52
Issue 18
Start page 10481
End page 10499
Total pages 19
Place of publication Washington, DC, United States
Publisher American Chemical Society
Language eng
Formatted abstract
The temperature dependence of the structures of a wide range of mixed-cation Tutton’s salts of general formula K2xRb2–2x[Cu(H2O)6](SeO4)2 has been determined over the temperature range 90 to 320 K. Crystals with a high proportion of potassium adopt a different structure (form B) from those with a low ratio (form A). In both forms, the [Cu(H2O)6]2+ ion has an orthorhombically distorted tetragonally elongated coordination geometry, but the long and intermediate bonds occur with a different pair of water molecules in form A compared with form B. The alkali metal is surrounded by seven close oxygen atoms in form B but eight oxygen atoms in form A, and this difference in coordination number is associated with the change in the Cu–O bond distances via the hydrogen-bonding network. For crystals with between 32 and ~41% potassium, a relatively sharp change from form B to A occurs on cooling, and the temperature at which this occurs increases approximately linearly as the proportion of potassium falls. For the whole range of mixed crystals, the bond lengths have been determined as a function of temperature. The data have been interpreted as a thermal equilibrium of the two structural forms of the [Cu(H2O)6]2+ ion that develops gradually as the temperature increases, with this becoming more pronounced as the proportions of the two cations become more similar. The temperature dependence of the bond lengths in this thermal equilibrium has been analyzed using a model in which the Jahn–Teller potential surface of the [Cu(H2O)6]2+ ion is perturbed by lattice strain interactions. The magnitude and sign of the orthorhombic component of this strain interaction depends upon the proportion of potassium to rubidium ions in the structure.
Q-Index Code C1
Q-Index Status Confirmed Code
Institutional Status UQ

Document type: Journal Article
Sub-type: Article (original research)
Collections: Official 2014 Collection
School of Chemistry and Molecular Biosciences
 
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Created: Mon, 30 Sep 2013, 23:18:16 EST by Mrs Louise Nimwegen on behalf of School of Chemistry & Molecular Biosciences