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Imidodiphosphates  ⊖ N[PO(OR) 2 ] 2  and Imidodiphosphonates  ⊖ N[POR 2 ] 2  are effective chelating ligands for a variety of metal cations including even Na ⊕ , for which a lipophilically wrapped hexameric polyion cluster has been structurally characterized. The corresponding hexameric lithium and polyrubidium ion complexes reported here exhibit considerable structural differences: The rather small Li ⊕  cations of coordination number five and tetraphenylimidodiphosphate form an isolated hexameric aggregate analogous to the Na ⊕  one, whereas the larger Rb ⊕  with coordination number seven and (3,4-dimethylphenyl)substituents crystallizes as a chain polymer. Based on the crystal structures, the dominant Coulomb attractions between cations and anions, the spatial requirement of the ligands and the essential phenyl/phenyl interactions in their lipophilic skin are discussed

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Wechselwirkungen in Molekülkristallen, 156 [1, 2]. Kristallzüchtung und Strukturbestimmung von (Imidodiphosphat)-Alkalisalzen mit Kationen niedriger und hoher Koordinationszahlen / Interaction in Molecular Crystals, 156 [1, 2]. Crystal Growth and Structure Determination of Alkali(imidodiphosphate) Salts with Cations of Low and High Coordination Numbers