Collection of Czechoslovak Chemical Communications - digital archive 

Abstract

In these crystal structures, the relatively weak electrostatic interactions between the bulky CB₁₁Me₁₂^- anion and the title cations permit cation-π interactions in the solid state. In all cases, single-crystal X-ray diffraction analysis reveals η⁶-arene-cation interactions within 10% of the expected van der Waals distance. The Tl⁺, Cs⁺, Rb⁺, and K⁺ structures are isomorphous, with the benzene molecules sandwiching the cation and four anions equatorially disposed in a nearly square arrangement. Both the cation and the near-square of closest anions are positioned to interact favorably with the local dipoles of benzene. The smaller Na⁺ crystallizes in polymeric chains with a nearly tetrahedrally coordinated cation in van der Waals contact with two anions and two benzene molecules in a tilted-sandwich arrangement. The Li⁺ structure possesses two motifs, a simple van der Waals sandwich of a toluene molecule and an anion, and chains of half-occupied toluene-Li complexes on inversion centers between anions. The simple van der Waals model is reasonably accurate for the cation-arene distances, only slightly underestimating the separation (2-10% deviation), with worse agreement for the smaller cations.

Keywords: Crystal structure determination; Noncovalent interactions; Cation-π interactions; Carborane anions; Boranes; Carboranes; Sandwich complexes; Arenes; Alkali metal cations.