A small series of biaryl ether containing cyclic peptidic scaffolds was synthesized and cyclized by an S<sub>N</sub>Ar reaction. The structure of one rigid scaffold was solved by X-ray crystallography and also determined in solution by NMR spectroscopy. Molecular alignment of the peptidic scaffold in strained PH polymer gels in [D<sub>6</sub>]DMSO was applied to extract residual dipolar couplings (RDCs). The RDC values were used to obtain a structure that was compared to the crystal structure. Good correlation was obtained, indicating that the RDC method represents a very precise structure determination method for small organic molecules in solution
