| Summary: | In the title complex salt, [Au2{(C6H5)2PCH2P(C6H5)2}]Cl2·(CH3)2C=O·H2O, the dication forms an eight-membered {—PCPAu}2 ring with a transannular aurophilic interaction [Au...Au = 2.9743 (2) Å]. The ring approximates a flattened boat conformation, with the two methylene C atoms lying ca 0.58–0.59 Å above the least-squares plane defined by the Au2P4 atoms (r.m.s. deviation = 0.0849 Å). One Cl− anion functions as a weak bridge between the AuI atoms [Au...Cl = 2.9492 (13) and 2.9776 (12) Å]. The second Cl− anion forms two (water)O—H...Cl hydrogen bonds about a centre of inversion, forming a centrosymmetric eight-membered {...HOH...Cl}2 supramolecular square. Globally, the dications and loosely associated Cl− anions assemble into layers lying parallel to the ac plane, being connected by C—H...Cl,π(phenyl) interactions. The supramolecular squares and solvent acetone molecules are sandwiched in the inter-layer region, being connected to the layers on either side by C—H...Cl,O(acetone) interactions.
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