Guest-host copper(I, II) complex Rb11[Cul(H2O)2][Cul 15 1 Cl24(CuIICl6)]. effect of the nature of the [Cu 2 1 (H2O)2]2+ guest on crystal structure formation

The crystals of {Rb₁₁[Cu ₂ ¹ ( H₂O)₂]}[Cu ₁₅ ¹ Cl₂₄(Cu^IICl₆)] (I) formed in the RbCl-CuCl-H₂O -( O₂, C₂H₂ ) system were studied by X-ray diffraction analysis and ESR spectroscopy. The cell is monoclinic, space group B2/m, Z = 2, a = 24.787(3), b = 13.126(2), c = 11.318(5) Å, γ = 122.36(1)? (DARCH automatic diffractometer, γ(MoKgα). The crystal structure of compound I is a guest-host type structure consisting of the {[Cu ₁₅ ¹ Cl₂₄Cu₁₁Cl₆]^13?}n anion layers oriented perpendicularly to the [010] direction and containing large octahedral cavities (edge length =12 Å) with a discrete [ Cu^IICl₆ ] octahedron lying inside the cavity. The Rb⁺ cations and the charged [Cu ₂ ¹ ( H₂O)₂]²⁺ guest species lie between the anion layers. The effect of the nature of the guest on host structure formation is considered using compounds I and Rb₁₁[Cu ₁₅ ¹ Cl₁₆Brd₆Cu^IICl₆ ) Cu-C=CH] as examples.