Coordination of a Central Atom by Multiple Intramolecular Pnicogen Bonds.

A central pnicogen Z atom (Z = Sb, As) is covalently attached to the O atom of three -O(CH)X chains where X represents either an aldehyde or amine group. The chain can fold around so that the basic X group can engage in a noncovalent pnicogen bond with the central Z. The formation of up to three pnicogen bonds is energetically favored. The amine appears to engage in stronger pnicogen bonds than does the aldehyde, and bonds to Sb are favored over As, but there is little dependence on the length of the chain. The formation of each successive pnicogen bond reduces the magnitude of the σ-holes surrounding the Z atom, which tends to weaken the attraction for the basic end of the chain.