The resonances of H-18b (left) as well as H-14 and H-11b (right) in strychnine (500 MHz, CDCl3) exemplify two seemingly straightforward yet challenging and frequently occurring situations in HNMR spectral interpretation: mismatch of visual multiplicity and spectral overlap. The resonance pattern of H-18b clearly does not match the first-order coupling tree of the true coupling constants that underlie this multiplet, as determined by QM analysis (observed spectrum in blue, calculated spectrum in red, residual in green; see also S3, Supplementary Material). For example, H-14 shows six J-couplings to H-15a, H-15b, H-16, H-20a, H-20b, and H-22. Collectively, this exemplifies the paradigm that peak frequency differences are not coupling constants (see Section 3.1 for explanation of this paradigm). Moreover, while H-11b can be readily assigned to the dd-type multiplicity at lower frequency, the broad, rather undefined resonance of H-14 eludes further interpretation. QM-based (S3, Supplementary Material) analysis reveals the origin of its generated peak pattern, which normally would be characterized as a broad singlet or multiplet, whereas HiFSA shows that it contains no less than 64 underlying lines (and far more transitions).