The structures of cyclopropane rings which carry σ‐acceptor or σ‐donor substituents have been studied using density‐functional theory (DFT), and mean bond lengths and conformational parameters retrieved from the Cambridge Structural Database. It is confirmed
that σ‐acceptor substituents, e.g. halogens, generate positive ring bond‐length asymmetry in which there is lengthening of the distal bond (opposite to the point of substitution), and shorterning of the two vicinal bonds. This is due to withdrawal of electron density
from the cyclopropane 1e′′ orbitals, which are bonding for the distal bond and antibonding for the vicinal bonds. For σ‐donor substituents such as SiH3 or Si(CH3)3, the DFT and crystal structure data show negative ring bond‐length
asymmetry (distal bond shortened, vicinal bonds lengthened), owing to electron donation into the 4e′ ring orbital, which are also bonding for the distal bond and antibonding for the vicinal bonds. The results also show that —OH substituents induce weak positive asymmetry,
but that the effects of methyl or amino substituents are either non‐existent or extremely small, certainly too small to measure using crystal structure information.