Rational Modification of the Hierarchy of Intermolecular Interactions in Molecular Crystal Structures by Using Tunable Halogen Bonds



A family of 16 isomolecular salts (3-XpyH)2[MX′4] (3-XpyH=3-halopyridinium; M=Co, Zn; X=(F), Cl, Br, (I); X′=Cl, Br, I) each containing rigid organic cations and tetrahedral halometallate anions has been prepared and characterized by X-ray single crystal and/or powder diffraction. Their crystal structures reflect the competition and cooperation between non-covalent interactions: N[BOND]H⋅⋅⋅X′[BOND]M hydrogen bonds, C[BOND]X⋅⋅⋅X′[BOND]M halogen bonds and π–π stacking. The latter are essentially unchanged in strength across the series, but both halogen bonds and hydrogen bonds are modified in strength upon changing the halogens involved. Changing the organic halogen (X) from F to I strengthens the C[BOND]X⋅⋅⋅X′[BOND]M halogen bonds, whereas an analogous change of the inorganic halogen (X′) weakens both halogen bonds and N[BOND]H⋅⋅⋅X′[BOND]M hydrogen bonds. By so tuning the strength of the putative halogen bonds from repulsive to weak to moderately strong attractive interactions, the hierarchy of the interactions has been modified rationally leading to systematic changes in crystal packing. Three classes of crystal structure are obtained. In type A (C[BOND]F⋅⋅⋅X′[BOND]M) halogen bonds are absent. The structure is directed by N[BOND]H⋅⋅⋅X′[BOND]M hydrogen bonds and π-stacking interactions. In type B structures, involving small organic halogens (X) and large inorganic halogens (X′), long (weak) C[BOND]X⋅⋅⋅X′[BOND]M interactions are observed with type I halogen–halogen interaction geometries (C[BOND]X⋅⋅⋅X′ ≈ X⋅⋅⋅X′[BOND]M ≈155°), but hydrogen bonds still dominate. Thus, minor but quite significant perturbations from the type A structure arise. In type C, involving larger organic halogens (X) and smaller inorganic halogens (X′), stronger halogen bonds are formed with a type II halogen–halogen interaction geometry (C[BOND]X⋅⋅⋅X′ ≈180°; X⋅⋅⋅X′[BOND]M ≈110°) that is electrostatically attractive. The halogen bonds play a major role alongside hydrogen bonds in directing the type C structures, which as a result are quite different from type A and B.