1H/17O Chemical Shift Waves in Carboxyl-Bridged Hydrogen Bond Networks in Organic Solids.

We report solid-state H-1 and O-17 NMR results for four O-17-labeled organic compounds each containing an extensive carboxyl-bridged hydrogen bond (CBHB) network in the crystal lattice: tetrabutylammonium hydrogen di-[O-17(2)]salicylate (1), [O-17(4)]quinolinic acid (2), [O-17(4)]dinicotinic acid (3), and [O-17(2)]Gly/[O-17(2)]GlyHCl cocrystal (4). The H-1 isotropic chemical shifts found for protons involved in different CBHB networks are between 8.2 and 20.5 ppm, which reflect very different hydrogen-bonding environments. Similarly, the O-17 isotropic chemical shifts found for the carboxylate oxygen atoms in CBHB networks, spanning a large range between 166 and 341 ppm, are also remarkably sensitive to the hydrogen-bonding environments. We introduced a simple graphical representation in which H-1 and O-17 chemical shifts are displayed along the H and O atomic chains that form the CBHB network. In such a depiction, because wavy patterns are often observed, we refer to these wavy patterns as H-1/O-17 chemical shift waves. Typical patterns of H-1/O-17 chemical shift waves in CBHB networks are discussed. The reported H-1 and O-17 NMR parameters for the CBHB network models examined in this study can serve as benchmarks to aid in spectral interpretation for CBHB networks in proteins.