An explanation is presented for the unusual conformations of some molecules that contain the C=C-C=C core, namely, butadienes, biphenyls, and styrenes. Small substituents often induce a synclinal conformation, which brings the substituents into close proximity, and sometimes, there is no anticlinal minimum at all. This would not be predicted from steric repulsion arguments nor would it be expected that atoms that are nonbonded in a Lewis structure would approach closer than the sum of their van der Waals radii. Atomic energies calculated according to the quantum theory of atoms in molecules (QTAIM) do not show a consistent pattern for these structurally similar molecules, nor are intersubstituent bond paths consistently found, nor favorable diatomic interaction energies calculated using the interacting quantum atoms (IQA) scheme. Instead, the synclinal conformations are found to be driven by the attraction energy of the electron distribution of the carbon atoms and the nuclei of the molecule.