Charge transfer in mixed-valence solids. Part II. Formula and structural variations in chlorocuprates(I,II)

Abstract

Hexamminecobalt(III) chlorocuprate(I,II) salts containing copper(I) and copper(II) in all proportions have been prepared and analysed. X-Ray powder diagrams and far-infrared spectra of the compounds are reported. The variation of formulae and structures with mole fraction of the two copper valence states is ascribed to coalescence of CuCl₄^3– ions into Cu₅Cl₁₆^11–; statistical formulae are derived on this basis and tested against the experimental analytical data.