Menshutkin Complexes: Influence of pnictogen, halide and arene on Pn···πarene interactions in [(PnX3)2{(2‐R‐C6H4)C2H4(2‐R‐C6H4)}]

More than 100 years ago B. N. Menshutkin systematically studied phase diagrams of antimony(III) halides with aromatic hydrocarbons for the first time, leading to the discovery of what is known today as Menshutkin complexes. As an extension to the wide variety of these Pn···πarene type complexes, which has been nicely reviewed by H. Schmidbaur and A. Schier in 2008, we report on a series of isomorphous compounds with diphenylethane derivatives as organic linkers in supramolecular networks. By setting up a library of complexes consisting of PnX3 (Pn = Sb, Bi; X = Cl, Br) and (2‐R‐C6H4)C2H4(2‐R‐C6H4) (R = Me, Br, NH2, NO2) we were able to compare the structures of five new Menshutkin complexes and additionally isolate six Sb···R donor‐acceptor type complexes. Lewis basic R‐groups favour the formation of donor‐acceptor complexes whereas weaker ones lead to Pn···πarene complexes. The influence of the pnictogen atom (Pn), the halide (X) and the substituent (R) concerning Pn···πarene distances in the solid state of the isomorphous Menshutkin complexes are examined. The results are discussed in view of previous studies providing a deeper insight into the qualitative and quantitative nature of Pn···πarene interactions.