However, the Z-(S)-(M)-(Sa) configuration of BR-1 proved already that the second isomer enriched in apolar solution inherits the same double bond configuration and opposite axial chirality of the biaryl moiety as compared to CR-1. These two structural features are indeed the ones expected for isomer CT-1. Only the (M)-helicity found in the co-crystal was not matching the expected more stable (P)-helicity of CT-1 leading to the presence of BR-1 instead. This unexpected capture of the instable helix in the condensed phase is most likely the result of crystal packing effects in the cocrystal, which leads to a nearly perfect structural overlap between CR-1 and BR-1 in the solid state (see details of the co-crystal elucidation in the Supporting Information). Thermal helix inversion is a highly dynamic process and thus is not inhibited kinetically if the higher energy of the unfavorable helix can be compensated. Indeed, when spectroscopically analyzing the corresponding solution mixture it became evident that in solution the second isomer is in fact CT- UV/Vis, and especially ECD spectroscopy together with theoretical analysis allowed us to unambiguously identify the expected Z-(S)-(P)-(Sa) configuration of CT-1 for the isomer strongly enriched in apolar solvents (Figure ). First, a clear identification of double bond and atropisomer configuration was achieved using Nuclear Overhauser effect (NOE) NMR spectroscopy (Figure ). Close proximity between the triazole proton 31 and the isolated biaryl proton 24 confirmed Z configuration of isomer CR-1 and residing of the biaryl-oxygen atom within the same molecular half-space as the sulfoxide oxygen atom, i.e. (Ra)-configuration of the biaryl axis. Correspondingly, proximity of triazole proton 31 to the opposite facing biaryl protons 20 and 22 evidenced Z configuration of the double bond and (Sa)-configuration of the axially chiral biaryl within CT-1.