The Dominant Role of Chalcogen Bonding in the Crystal Packing of 2D/3D Aromatics

The chalcogen bond is a nonclassical σ‐hole‐based noncovalent interaction with emerging applications in medicinal chemistry and material science. It is found in organic compounds, including 2D aromatics, but has so far never been observed in 3D aromatic inorganic boron hydrides. Thiaboranes, harboring a sulfur heteroatom in the icosahedral cage, are candidates for the formation of chalcogen bonds. The phenyl‐substituted thiaborane, synthesized and crystalized in this study, forms sulfur⋅⋅⋅π type chalcogen bonds. Quantum chemical analysis revealed that these interactions are considerably stronger than both in their organic counterparts and in the known halogen bond. The reason is the existence of a highly positive σ‐hole on the positively charged sulfur atom. This discovery expands the possibilities of applying substituted boron clusters in crystal engineering and drug design. Chalcogen bonds of thiaboranes were found to be considerably stronger than σ‐hole bonds in organic compounds. The reason is the highly positive belt of σ‐holes on the positively charged sulfur atom. The charge distribution is the driving force for chalcogen bonding of thiaboranes.