On verdigris, part II: synthesis of the 2-1-5 phase, Cu-3(CH3COO)(4)(OH)(2)center dot 5H(2)O, by long-term crystallisation from aqueous solution at room temperature

摘要

Long-term crystallisation from aqueous copper(ii)-acetate solution after the addition of ammonia at 25 degrees C led to the formation of a hitherto poorly characterised phase in the verdigris pigment system Cu(CH3COO)(2)-Cu(OH)(2)-H2O. Laboratory X-ray powder diffraction (XRPD) was successfully employed to solve the crystal structure. The structure solution reveals a phase composition of the Cu-3(CH3COO)(4)(OH)(2)center dot 5H(2)O 2-1-5 phase, which was also confirmed by thermal analysis. The 2-1-5 phase crystallises in space group P2(1)/c (14) with lattice parameters of a = 12.4835(2) angstrom, b = 14.4246(2) angstrom, c = 10.7333(1) angstrom and beta = 102.871(1)degrees. The crystal structure consists of Cu-2(CH3COO)(2)(CH3COO)(1/2)(OH)(4/3)H2O1/6+ dimers that are interconnected by Cu(CH3COO)(CH3COO)(1/2)(OH)(2/3)(1/6-) squares forming chains running in the c-direction. Non-coordinating hydrate water molecules are intercalated inbetween the chains and mediate the inter-chain interaction. IR and Raman spectroscopy techniques were also employed to confirm selected aspects of the determined crystal structure. The magnetic properties of the 2-1-5 phase decompose into two independent subsystems: a strongly antiferromagnetically spin exchange coupled magnetic Cu-Cu dimer and a significantly weaker coupled Cu monomer. The light blue colour of the sample originates from a reflectance maximum at 488 nm and significantly differs from the known verdigris phases. An investigation of several historic verdigris pigment samples revealed that this phase occurs both as a minor and a major component. Hence, our reference data for the title compound will help to improve the understanding of the multiphase mixtures occurring in historic verdigris samples.