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Treatment of N,N′-methylenedipyridinium dichloride [C5H5N-CH2-NC5H5]Cl2 with MCl2 (M = Zn or Cd) in aqueous solution gives the organic-inorganic hybrid ionic compounds [C5H5N-CH2-NC5H5] · [MCl4]. Both complex salts were fully characterised by multinuclear NMR spectroscopy, elemental analysis, and their molecular structures confirmed by powder X-ray diffraction studies. The most striking feature in both solid state structures was the presence of the C…Cl-M short contacts between the organic [C5H5N-CH2-NC5H5] dication and inorganic [MCl4] anion, which led to different crystal packing. For [C5H5N-CH2-NC5H5]·[ZnCl4], the C…Cl-Zn interactions led to the alternating arrangement of [C5H5N-CH2-NC5H5]2+[ZnCl4]2− to form 1-D chains in the direction [010], and each individual chain had a two-fold rotational axis along the b axis, while for [C5H5N-CH2-NC5H5] · [CdCl4] the C…Cl-Cd associations gave 2-D network. In both solid state structures, the presence of Cl-ring centroid distances gave a strong indication of some form of Cl-π interactions.

chemical papers

Synthesis and crystal and molecular structures of N,N′-methylenedipyridinium tetrachlorozincate(II) and N,N′-methylenedipyridinium tetrachlorocadmate(II)