Synthesis, crystal and electronic structure of [Hg(7)As(4)](AgI(3))(2), a novel supramolecular complex with the off-plane AgI(3)(2-) guest anionстатья
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Аннотация:A novel supramolecular inorganic complex [Hg(7)As(4)](AgI(3))(2) has been prepared and its crystal structure determined. It crystallizes in the cubic system (space group Pa (3) over bar) with the unit cell parameter a = 13.138(1) Angstrom and Z = 4. The crystal structure comprises a three-dimensional positively charged host framework [Hg(7)As(4)](4+) with AgI(3)(2-) guest anions trapped in each cavity of the framework. The guest anion shows an unusual off-plane geometry (C(3v) symmetry), with a large, anisotropic thermal displacement parameter for the silver atom, which lowers significantly upon cooling from 293 down to 120 K. A study of the electronic structure shows that, although the host-guest interaction is weak and diffuse, it governs both the geometry of the guest anion and its positioning within the framework cavities. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2003).