5-amino-2-methylpyridinium hydrogen fumarate: An XRD and NMR crystallography analysis

Abstract

Single-crystal X-ray diffraction structures of the 5-amino-2-methylpyridinium hydrogen fumarate salt have been solved at 150 and 300 K (CCDC 1952142 and 1952143). A base-acid-base-acid ring is formed through pyridinium-carboxylate and amine-carboxylate hydrogen bonds that hold together chains formed from hydrogen-bonded hydrogen fumarate ions. ¹ H and ¹³ C chemical shifts as well as ¹⁴ N shifts that additionally depend on the quadrupolar interaction are determined by experimental magic angle spinning (MAS) solid-state nuclear magnetic resonance (NMR) and gauge-including projector-augmented wave (GIPAW) calculation. Two-dimensional homonuclear ¹ H-¹ H double-quantum (DQ) MAS and heteronuclear ¹ H-¹³ C and ¹⁴ N-¹ H spectra are presented. Only small differences of up to 0.1 and 0.6 ppm for ¹ H and ¹³ C are observed between GIPAW calculations starting with the two structures solved at 150 and 300 K (after geometry optimisation of atomic positions, but not unit cell parameters). A comparison of GIPAW-calculated ¹ H chemical shifts for isolated molecules and the full crystal structures is indicative of hydrogen bonding strength.

Keywords: GIPAW; MAS; NMR crystallography; hydrogen bonding.