Abstract
The polarised single-crystal electronic spectra of CaCu(AcO)4,6H2O are assigned in S4 and D2d symmetries, with a dxy ground state and yield the one-electron orbital sequence: dxy > dz2 > dxz, dyz > dx2–y2. The e.s.r. spectra yield the orbital reduction factors r⊥= 0·78 and r∥= 0·926 . That r∥ > r⊥ indicates substantial out-of-plane bonding of the long-bonded acetate oxygen atoms. These results suggest that the molecular structure of CaCu-(AcO)4,6H2O should be described as a distorted dodecahedron (rather than as a distorted tetrahedron or octahedron) involving an eight co-ordinate copper(II) ion environment. Bond-length and electronic energy-level data, in support of this suggestion, are discussed and compared with related systems.
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