X-Ray structural investigations of a bisparaphenylene-34-crown-10 derivative (BPP34C10) and its 1:1:1 complex with [Diquat][PF6]2 and H2O reveal that, of two crystallographically independent conformations (I and II) both supporting large molecular cavities, one (II) retains its gross shape on complexation and interacts with the [Diquat]2+ dication by means of hydrogen and electrostatic bonds whilst accommodating weak charge transfer interactions and a hydrogen bonded H2O molecule within the docking constraints and microcavity, respectively, imposed by the more dominant non-covalent forces.