Interplay of Ionic Species in Salts of Homoleptic Quaternary Phosphonium Cations Bearing Linear Biphenyl Moieties

Quaternary phosphonium salts are popular candidates used in many chemical transformations and synthetic chemistry, notably catalysis. We have examined the single crystals of two bulky compounds, tetra([1,1′-biphenyl]-4-yl) dicyanamide (C48H36P+·N(CN)2−, compound 1), bromide hydrate (C48H36P+·Br−, CH3CN, H2O, 2), herein report structural properties for compounds with an emphasis on influence ion-ion interaction towards self-assembly; overall self-assembly both structures is very similar, subtle differences cell parameters. The symmetrical tetra ([1,1′-biphenyl]-4-yl) cations self-assembled to form robust stacked columns solid-state, voids occupied by anions or solvent molecules. Quantitative examination intermolecular interactions using Hirshfeld surface analysis found that classical non-classical hydrogen bonding appears be dominant contributor stabilizing cases. present work can not only benefit understanding mutual between sterically encumbered counterions, but also provide insights arrays solid-state.