Four novel 2,3-naphtho-15-crown-5 (N15C5) and 2,3-naphtho-18-crown-6 (N18C6) complexes [Na(N15C5)]2[Pd(SCN)4] (1), [Na(N15C5)]2[Pt(SCN)4] (2), [K(N18C6)]2[Pd(SCN)4] (3) and [K(N18C6)]2[Pt(SCN)4] (4) were synthesized and characterized by elemental analysis, FT-IR spectra and single-crystal X-ray diffraction. The structure analyses reveal that both 1 and 2 are assembled into zigzag chains by the strong intermolecular π–π stacking interactions between adjacent 2,3-naphthylene groups of N15C5. The molecules of complexes 3 and 4 are linked into 1D chains by the bridging K–O(ether) interactions between the adjacent [K(N18C6)]+ units and the resulting chains are constructed into a novel 2D network by inter-chain π–π stacking interactions between the neighboring 2,3-naphthylene moieties of N18C6. According to the supramolecular self-assemblies of complexes 1–4, two types of stacking model of naphthylene groups are given and discussed.
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