Proton shielding tensors in potassium hydrogen maleate

Abstract

The proton NMR in single crystals of potassium hydrogen maleate has been sttudied by means of multiple-pulse line-narrowing techniques. The magnetic shielding tensors of all magnetically inequivalent protons in the unit cell could be determined independently. Two of these protons are carboxylic, forming hydrogen bonds. The orientations of the shift tensors are consistent with the position of the hydrogens at the midpoints of the 0–0 intervals. The range of anisotropy of 32 ppm, found for the shift tensor of the caboxylic hydrogen, is larger than that found for hydrogen bonds in acids and seems to be characteristics of acidic salts. The other protons in the unit cell are olefinic. Two features distinguish this type of protons from those studied so far: (1) The magnetic shielding tensor is not even approximately axially symmetric, the principal values being −2.4, −5.1, −7.3 ± 05 ppm (from adamantane); and (2) the principal directions reflect all characteristic directions of the carboncarbon double bond (while the CH direction is of no importance). The principal value in the direction perpendicular to the sp 2 system is the least shielded one.