The stereochemistry of quaternary N-methyl sparteinium cations, their derivatives, stereoisomers and analogues : Part II. Molecular and crystal structure, and IR spectra of methiodide and methperchlorate of 2-oxosparteine

Abstract

The crystal and molecular structures of two quarternary salts of 2-oxosparteine (II), the methiodide (IICH + 3 • I −) and the methperchlorate (IICH + 3 • ClO − 4) have been determined on the basis of X-ray and IR data. The studies were performed by analogy to previously investigated quaternary salts of sparteine (I), the methiodide (ICH + 3 • I −) and the methperchlorate (ICH + 3 • ClO − 4). As expected, the configurations and conformations of cationic parts within the two pairs of quaternary salts are identical, except for the structure of their A/B fragments, which in ICH + 3 cations have the character of tertiary amines, but in IICH + 3 that of lactams. On the basis of accumulated X-ray and IR data the similarities and differences in the modes of interaction of perchlorate and iodide anions with quaternary cations, and especially with their N +CH 3 groups are discussed. In this discussion are also included the methiodide and methperchlorate of α-isosparteine: IIICH + 3 • X − (X − = I − or ClO − 4) where N +CH 3 groups are cisoidally oriented to the basic nitrogen atoms. The most interesting observations are as follows: (i) When N +CH 3 groups are easily accessible for direct quasi hydrogen bonding interactions with counter anions and when other positive charged groups, for instance lactam groups, are absent in quaternary cations, perchlorate anions interact more strongly than the iodide anions and in consequence introduce conformational changes into the ring with N +CH 3 group as well as into further rings. (ii) Perchlorate and iodide anions interact with N +CH 3 groups similarly and very weakly if at all, when the N +CH 3 groups are for steric reasons inaccessible to counter anions or when in quaternary cations there are additional groups which attract the counter anions electrostatically. The last mechanism operates in both quaternary salts of 2-oxosparteine and this is the reason why their monocrystals are isosteric and IR spectra almost identical. (iii) The sterically hindered N +CD 3 groups in both IIICD + 3 • X − salts give rise in their IR spectra to two doubles of sharp, well resolved bands which indicate the presence of two different rotamers stabilized by two modes of weak intramolecular hydrogen bonds with basic N atoms. (iv) In IIICH + 3 • X − and IIICD + 3 • X − salts the perchlorate and iodide anions do not interact at all with the rotating and vibrating N +CH 3 (N +CD 3) group but the structures of these salts are not isosteric since the perchlorate anions interact more strongly than iodide anions with the A/B fragment of the IIICH + 3 cations. This is visible from the shapes and intensities of the so-called “ trans” band in the IR spectra of both salts.