Bowing to the Pressure of π⋅⋅⋅π Interactions: Bending of Phenyl Rings in a Palladium(II) Thioether Crown Complex

Compression of a parallel four‐fold phenyl embrace involving two cations in [Pd([9]aneS 3 )(PPh 3 ) 2 ](PF 6 ) 2 ([9]aneS 3 =1,4,7‐trithiacyclononane) leads to π⋅⋅⋅π stacking interactions and concomitant pyramidalization at the ipso carbon atom of one of the phenyl rings. These pressure‐induced transformations have been rationalized by Hirshfeld surface analysis, density functional calculations and natural bond orbital analysis.