Does Hydrogen Bonding Matter in Crystal Engineering? Crystal Structures of Salts of Isomeric Ions

Abstract The preparation and structure determinations of the crystalline salts [3,3′‐H 2 bipy][PtCl 4 ] ( 2 ), [2,2′‐H 2 bipy][PtCl 4 ] ( 3 ) and [1,4′‐Hbipy][PtCl 4 ] ( 4 ) and [3,3′‐H 2 bipy][SbCl 5 ] ( 6 ) and [1,4′‐Hbipy][SbCl 5 ] ( 8 ) are reported. In addition a redetermination of the structure of the metastable salt [4,4′‐H 2 bipy][SbCl 5 ] ( 5 b ) in the corrected space group Pbcm is described. These structures are compared to those of the known salt [4,4′‐H 2 bipy][PtCl 4 ] ( 1 ), the stable triclinic form of [4,4′‐H 2 bipy][SbCl 5 ] ( 5 a ) and [2,2′‐H 2 bipy][SbCl 5 ] ( 7 ). In the case of the salts of the rigid [PtCl 4 ] 2− ion, structures 2 , 3 and 4 are essentially isostructural despite the differing hydrogen‐bonding capability of the cations. Similarly, among the salts of [SbCl 5 ] 2− ions, structures 7 and 8 are essentially isostructural. Structure 6 differs from these in having a differing pattern of aggregation of the [SbCl 5 ] 2− ions to form polymeric rather than tetrameric units. It is evident that local hydrogen‐bonding interactions, although significant, are not the only or even the decisive influence on the crystal structures formed by these salts. These observations are not in good accord with the heuristic “sticky tecton” or supramolecular synthon models for synthetic crystallography or crystal engineering.