Novel supramolecular cyclohexane-like structures, [NiL2] (1) and [ZnL2] (2) (HL=acetylferrocenyl thiosemicarbazone), have been constructed by self-assembly of ferrocene moieties ia aromatic C–H···π interactions. The
nickel(II) atom in 1 is coordinated in a distorted square-planar cis configuration with two ferrocene-containing
ligands positioned on the same side. One of the ferrocene moieties interacts with symmetry-related species to form a supramolecular arrangement that is topologically equivalent to cyclohexane, but in which edge-to-face C–H···π interactions between ferrocene moieties serve the same structural functions as the C–C bonds in cyclohexane. The zinc(II) atom in 2 is coordinated in a tetrahedral geometry with two equivalent Zn–S and Zn–N bonds. Each
ferrocene moiety interacts with symmetry-related species using C–H···π interactions to form a two-dimensional
cyclohexane-like network. Powder X-ray diffraction analyses of complexes 1 and 2, together with the palladium(II) complex [PdL2] (3), copper(II) complex [CuL2] (4), and cobalt(II) complex [CoL2] (5) reveal that the supramolecular cyclohexane-like aggregation is robust enough to be exchanged from one network to another. All the results indicate that although C–H···π interactions have energies only in the 2–20 kJ mol−1 range, these interactions are directional enough in combination that the orientation
of molecules in the
solid can be predicted with a reasonable degree of accuracy.
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