Abstract
Two new inorganic/organic salts based on diphosphopentamolybdate (1 and 2) are grown from aqueous solution in the presence of p‐phenylenediamine (ppda). Their crystal structures demonstrate the role of non‐bonding interactions in the crystal engineering of these solids. In 1 crystal packing is dominated by two kinds of supramolecular assemblies: an unusual octadecameric water cluster and a H‐bonded dimer formed between ppda cation and diphosphopentamolybdate anion. In 2 supramolecular water‐organic motifs envelop phosphomolybdate anions from either side through H‐bonding. Crystal structures of 1 and 2 revealed that diphosphopentamolybdate shows strong affinity for H‐bonding and the extent of protonation and cation‐anion ratio probably dictates the formation of hydrophilic pockets to facilitate clustering of water molecules.
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