Discrimination in resolving systems. VI. Comparison of the diastereomers of deoxyephedrinium and ephedrinium 4′-fluoromandelates

(−)‐(R)‐Deoxyephedrine forms poorly discriminating diastereomeric salts with 4′‐fluoromandelic acid from 95% ethanol. Both less‐soluble (L) (S)‐4′‐fluoromandelate and more‐soluble (M) (R)‐4′‐fluoromandelate phases are monoclinic and unsolvated. Their solubility ratio (M/L) in 95% ethanol is only 1.2, which correlates with the similarity and small differences in their respective heats of fusion and fusion temperatures. The (R)‐deoxyephedrinium and the related (1R;2S)‐ephedrinium 4′‐fluoromandelate systems show L‐salts with higher ion‐pair volumes and lower densities than their M‐salts. (R)‐Deoxyephedrinium salts have higher volumes than the comparable (1R;2S)‐ephedrinium salts even though the resolving base (R)‐deoxyephedrine lacks the benzylic hydroxy. In the solids, bilayered structures segregate polar and nonpolar molecular regions. The principle interionic interactions are hydrogen bonds between protonated secondary ammonium ions and carboxylates forming infinite chains with a six‐atom repeating unit H‐N+‐H···O‐C−‐O [C22(6)]. These are buttressed by mandelate hydroxy to carboxylate hydrogen bonds. Differing interactions between phenyl and 4′‐fluorophenyl rings in the nonpolar layers of the salts correlate with the density and stability inversion. Chirality 13:244–250, 2001. © 2001 Wiley‐Liss, Inc.