Chalcogen Bond versus Halogen Bond: Changing Contributions in Determining the Crystal Packing of Dihalobenzochalcogenadiazoles

In the crystals of 4,7-dihalobenzo[c][1,2,5]chalcogenadiazoles, the molecules are connected by two competing secondary bonding interactions: chalcogen bond (ChB) and halogen bond (HaB). Because the strengths of ChB and HaB change according to the kind of chalcogen (E: S, Se, Te) and halogen (X: Cl, Br, l), their relative contributions in determining the crystal packing can also change. Six newly determined crystal structures as well as 3 previously reported structures can be categorized into two groups: ChB-dominant and HaB-dominant structures. HaB in which X = I is strong enough to dictate the crystal packing of compounds with E = S and Se, but not where E = Te, whereas HaB in which X = Cl or Br has little effect on ChB-dominant molecular networks in crystals. The observed changing contributions of ChB and HaB may be useful for designing new supramolecular synthons for crystal engineering