Resolution of mandelic acid with (-)(R)-deoxyephedrine in 95% ethanol produces essentially nondiscriminating unsolvated binary mandelate salts. (R)deoxyephedrinium (R)-mandelate (I) is orthorhombic, P212121, a = 8.076(2) Å, b = 8.926(3) Å, c = 23.242(15) Å, V = 1675.3(14) Å3 , Z = 4. (R)-deoxyephedrinium (S)-mandelate (II) is monoclinic, P21, a = 16.061(14) Å, b = 8.902(8) Å, c = 19.585(20) Å, β = 111.76(8)°, V = 2600(4) Å3, Z = 6 with three ionpairs comprising the asymmetric unit. The principle interionic interactions are ribbon-like chains of salt-bridge hydrogen bonds which associate protonated secondary ammonium ions with carboxylates in I and II along crystallographic screw axes with a six-atom repeating unit H-N+-H ··· O-C--O [C22(6)]. The (R)-mandelate additionally shows intraion hydrogen bonding and the (S)-mandelate shows interanion hydrogen bonding. Solubilities (in 95% ethanol), fusion points and heats of fusion indicate essentially no diastereometric discrimination. From acetone, the (S)-mandelate salt forms a efflorescent hemiacetone solvated binary phase (III), triclinic, P1, a = 10.869(9) Å, b = 10.838(13) Å, c = 17.138(18) Å, α = 90.32(9)°, β = 91.34(8)°, γ = 108.20(8)°, V = 1917(4) Å3, Z = 4. Ions form hydrogen bonded chains similar to those in II; acetones are unassociated. In I, columns form with the polar hydrogen bonded chains at the core and nonpolar aryl rings radiating and interdigitating adjacent columns. Packing in II and III produces bilayers of alternating polar and nonpolar regions, with acetones of III in the nonpolar regions.
Citation: Pilot Scholars Version (Modified MLA Style)
Valente, Edward J.; Harris, M. E.; Goubitz, K.; and Schenk, H., "Deoxyephedrine -- mandelic acid diastereomers" (1999). Chemistry Faculty Publications and Presentations. Paper 20.