Z. Dega-szafran et al., C-13 CP MAS NMR, FTIR, X-ray diffraction and PM3 studies of some N-(omega-carboxyalkyl)morpholine hydrohalides, J MOL STRUC, 560(1-3), 2001, pp. 261-273
N-(omega -carboxyalkyl)morpholine hydrochlorides, OC4H8N(CH2)(n)COOH . HCl,
n = 1-5, were obtained and analyzed by C-13 cross polarization (CP) magic
angle spinning (MAS) NMR, FTIR and PM3 calculations. The structure of N-(3-
carboxypropyl)-morpholine hydrochloride (n = 3) has been solved by X-ray di
ffraction method at 100 K and refined to the R = 0.031. The crystals are mo
noclinic, space group P2(1)/c, a = 14.307(3), b = 9.879(2), c = 7.166(1) An
gstrom, beta = 93.20(3)degrees, V = 1011.3(3) Angstrom (3), Z = 4. In this
compound the nitrogen atom is protonated and two molecules form a centrosym
metric dimer, connected by two N+-H . . . Cl- (3.095(1) Angstrom) and two O
-H . . . Cl- (3.003(1) Angstrom) hydrogen bonds. C-13 CP MAS NMR spectra, c
ontrary to the solution, showed non-equivalence of the ring carbon atoms. T
he PM3 calculations predict a molecular dimer without proton transfer for a
n HCl complex, while for an HBr complex an ion pairs with proton transfer,
and reproduces correctly the conformation of both dimers but overestimates
H-bond distances. Shielding constants calculated from the PM3 geometry of i
on pairs gave a linear correlation with the C-13 chemical shifts in solids.
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