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Mixed crystals of tetrakis(3,4-dimethylphenyl)imidodiphosphate salts with alkalication ratios K ⊕ /Rb ⊕  (1:5) and Rb ⊕ /Cs ⊕  (1:1), (1:3) as well as (3:1) have been grown by suspending finely ground stoichiometric mixtures of alkali carbonates in toluene solutions of the strongly chelating ligand HN(PO(OR) 2 ) 2  - The cation ratios were measured by Total Reflexion X-Ray Fluorescence (TXRF) analysis and the single crystal structures of the polymeric K ⊕ /Rb ⊕  as well as the Rb ⊕ /Cs ⊕  imidodiphosphate salts determined by X-ray structure analysis. The selectivity of the various alkali ions for insertion in the crystal lattices of the individual imidodiphosphate salts has been confirmed by concentration-dependent crystallizations and discussed based on the structural analysis of the differing ligand conformations. The unit cell parameter dependence on the alkali cation radii provided information on van der Waals interactions between adjacent phenyl rings of the imidodiphosphate ligands and suggests the selective alkali cation insertion to be partly due to supramolecular repulsion within the lipophilic phenyl skin during the selfaggregation of the polymeric salt chains

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Wechselwirkungen in Molekülkristallen, 157 [1, 2]. Mischkristallzüchtung und Strukturbestimmungen von Tetra(3,4-dimethylphenyl)-imidodiphosphat-Salzen mit Alkalikation- Verhältnissen K ⊕ /Rb ⊕ (1:5) und Rb ⊕ /Cs ⊕ (1:1) / Interaction in Molecular Crystals, 157 [1, 2]. Mixed Crystal Growth and Structure Determinations of Tetrakis(3,4-dimethylphenyl)-imidodiphosphate Salts with Alkali Cation Ratios K ⊕ /Rb ⊕  (1:5) and Rb ⊕ /Cs ⊕  (1:1)