Abstract

We describe the crystallisation and crystal structure of (Ph₃P)₂Ag(O₂C₂O₂)Ag(PPh₃)₂, and analyse its crystal packing and crystal supramolecularity in the context of a set of six related molecules of the type (Ph₃P)₂M(X¹X³C₂X²X⁴)M(PPh₃)₂, M⊕=⊕Cu, Ag; Xⁱ⊕=⊕O, S. These molecules are heavily phenylated, and intramolecular and intermolecular motifs involving mainly edge-to-face (EF) phenyl rings are dominant. There are three different crystal packings (A, B, C) representing substitutional trimorphism, because the internal substitution does not necessarily influence crystal packing. There are intramolecular EF interactions between different Ph₃P ligands at the end and across the bridge of the complexes, and these intramolecular EF pairs mesh to generate many additional intermolecular EF motifs. The dominant multiple phenyl embraces are (EF)₄, (EF)_∞ ribbons, and (EF)₂(OFF) (OFF⊕=⊕offset-face-to-face), with one instance of triangular (EF)₃. The sixfold phenyl embrace (6PE) comprised of (EF)₆ occurs only in trimorph A, adopted by (Ph₃P)₂Ag(O₂C₂O₂)Ag(PPh₃)₂. Intramolecular and intermolecular C–H⋯X hydrogen bonding occurs, but is not a major influence. The mutual interactions of the intramolecular stereochemistry of the complexes and the crystal packing are discussed.