Abstract
Atomically resolved crystal structures not only suffer from the inherent uncertainty in accurately locating H atoms but also are incapable of fully revealing the underlying forces enabling the formation of final structures. Therefore, the development and application of novel techniques to illuminate intermolecular forces in crystalline solids are highly relevant to understand the role of hydrogen atoms in structure adoption. Novel developments in (1)H NMR MAS methodology can now achieve robust measurements of (1)H chemical shift anisotropy (CSA) tensors which are highly sensitive to electrostatics. Herein, we use (1)H CSA tensors, measured by MAS experiments and characterized using DFT calculations, to reveal the structure-driving factors between the two polymorphic forms of acetaminophen (aka Tylenol or paracetamol) including differences in hydrogen bonding and the role of aromatic interactions. We demonstrate how the (1)H CSAs can provide additional insights into the static picture provided by diffraction to elucidate rigid molecules.