4.1 Article

On Verdigris, Part III: Crystal Structure, Magnetic and Spectral Properties of Anhydrous Copper(II) Acetate, a Paddle Wheel Chain

Journal

ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE
Volume 645, Issue 15, Pages 988-997

Publisher

WILEY-V C H VERLAG GMBH
DOI: 10.1002/zaac.201900125

Keywords

Copper acetate; Structure elucidation; Carboxylate ligands; X-ray diffraction; Magnetic properties

Funding

  1. DFG [EG 137/9-1]

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Pure anhydrous Cu(CH3COO)(2) was obtained both, by thermal dehydration of Cu(CH3COO)(2)center dot H2O and by drying a commercially purchased mixture of Cu(CH3COO)(2)center dot H2O and Cu(CH3COO)(2) in a nitrogen atmosphere using P2O5 as drying agent. The crystal structure was solved ab initio from synchrotron X-ray powder diffraction (XRPD) data at 150 degrees C and from laboratory XRPD data at ambient conditions and found to be isotypic to anhydrous chromium(II), molybdenum(II) and rhodium(II) acetate. Cu(CH3COO)(2) crystallizes in space group P1 (no. 2) with lattice parameters of a = 5.1486(3) angstrom, b = 7.5856(6) angstrom, c = 8.2832(6) angstrom, alpha = 77.984(4)degrees, beta = 75.911(8)degrees, gamma = 84.256(6)degrees at ambient conditions. Cu-2(CH3COO)(4) paddle wheels with short (2.6 angstrom) Cu-Cu distances form chains in a direction, which is the main motif in the crystal structure. Due to their identical structural main motif Cu(CH3COO)(2)center dot H2O and Cu(CH3COO)(2) exhibit a similar bluish-green color, almost identical UV/Vis spectra and comparable magnetic properties. The temperature dependent magnetic susceptibility also indicates only weak inter-dimer spin exchange between neighbouring Cu-2(CH3COO)(4) paddle wheels.

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