Its Environment Engraves the Geometry of a Molecular Entity: Allyl Coordination within a Dicationic Ruthenium(IV) Complex

The best molecular
arrangements for [Ru­(η5-C5(CH5)5)­(η3-CH2CHCHC6H5)­(CH3CN)2]2+ (1) in various environments are determined.
The isolated compound 1a serves as a point of reference.
On the basis of crystal structure data, solid-state environments are
modeled by first placing the cationic compound into the appropriate
anionic environment 2a and then completing the unit cell
contents by addition of the solvent molecule 3a. Density
functional calculations (BP86) augmented by various dispersion corrections (BP86-D2, BP86-D3, BP86-D3­(BJ),
BP86-dDsC) establish the computational approach for electronic structure
and geometry optimization. According to the models considered, intermolecular
electrostatic interactions are to a major part responsible for substantial
changes in intramolecular arrangements.