X-ray structure and thermal analysis of a 1?1 complex between (S)-naproxen and heptakis(2,3,6-tri-O-methyl)-?-cyclodextrin

Caira, Mino R.; Griffith, Vivienne J.; Nassimbeni, Luigi R.; Oudtshoorn, Bosch van

doi:10.1007/bf00708773

Cited by 28 publications

(11 citation statements)

References 17 publications

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“…The heptagon's distances and angles, the distances of the O4n atoms from their mean plane and the tilt angles, that show the degree of tilting of the glucose residues with respect to the above mean plane, all vary widely among the residues and deviate from the corresponding parameters of the complexes of -cyclodextrin, which exhibits sevenfold symmetry. The tilting is towards the interior of the cavity, as in the inclusion complexes of TMCD/ethyl laureate (Mentzafos et al, 1994) and TMCD/methylcyclohexane (Rontoyianni et al, 1998) and in contrast to all the other TMCD complexes determined so far, where two glucose units tilt in the opposite sense (Harata et al, 1992;Caira et al, 1996;Brown et al, 1996;Caira et al, 1995;Harata et al, 1983Harata et al, , 1988. Table 2 refers also to the conformation of the methoxy groups.…”

Section: Figurementioning

confidence: 94%

“…Indeed, X-ray studies (Harata et al, 1984a(Harata et al, , 1987(Harata et al, , 1992Caira et al, 1996;Brown et al, 1996;Caira et al, 1995) have shown that the conformation of permethylated macrocycles can be remarkably distorted and the topology of the inclusion of optical antipodes is different (Harata et al, 1984b(Harata et al, , 1987(Harata et al, , 1988. However, the ability of CDs as agents for selective precipitation of one enantiomer from solutions of racemic mixtures has been very limited (Harata et al, 1988;Benshop & Van der Berg, 1970;Mokolajczyk & Drabowicz, 1971), except for the case of hexakis(2,3,6-tri-O-methyl)--cyclodextrin (permethylated CD, TMCD) and racemic 1,7-dioxaspiro-[5.5]undecane (1), where we have demonstrated that we can isolate exclusively the (R)-enantiomer (Yannakopoulou et al, 1996).…”

Section: Introductionmentioning

confidence: 99%

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Non-covalent interactions in the crystallization of the enantiomers of 1,7-dioxaspiro[5.5]undecane (olive fly sex pheromone) by enantiospecific cyclodextrin hosts, hexakis(2,3,6-tri-O-methyl)-α-cyclodextrin and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin

Makedonopoulou

Yannakopoulou

Mentzafos

et al. 2001

Acta Crystallogr Sect B

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The enantiomers of racemic olive fly sex pheromone 1,7-dioxaspiro[5.5]undecane (1) have been isolated by crystallization with enantiospecific cyclodextrin hosts: (S)-(1) crystallizes with heptakis(2,3,6-tri-O-methyl)-beta-cyclodextrin (TMbetaCD) and (R)-(1) with hexakis(2,3,6-tri-O-methyl)-alpha-cyclodextrin (TMalphaCD). The crystal structure of TMbetaCD/(S)-(1) from synchrotron radiation data at 100 K, determined for the first time, proves that TMbetaCD crystallizes with only the (S)-enantiomer from the racemic mixture. Comparison with the 100 K structure of TMalphaCD/(R)-(1) redetermined with synchrotron data has provided insight into the interactions between each of the hosts with the corresponding enantiomeric guests. Owing to the high resolution of the data and the unusually high quality of the crystals, localization of the H atoms has been achieved, a rare accomplishment for cyclodextrin X-ray structures. This made possible, apart from the geometry of the complexes, the detailed description of a five-membered-ring water cluster with very well ordered hydrogen bonding. The enantiospecificity exhibited by the described systems reveals the subtle differences of the weak intermolecular forces involved in the selective binding of the two optical antipodes by the two hosts. The binding geometry in the two complexes is different, but it is effected in both by numerous host-guest C-H.O interactions, resulting from induced fit of the hosts toward each of the enantiomeric guests. In TMalphaCD/(R)-(1) two of these H.O host-guest distances, directed toward the acetal O atoms defining the chirality of the guest, are much shorter than the rest and also shorter than all the H.O distances in TMbetaCD/(S)-(1). Moreover, (R)-(1) interacts not only with the enclosing host, but with other hosts in the crystal lattice, in contrast to (S)-(1) in the TMbetaCD/(S)-(1) complex which is isolated inside channels formed by the host molecules. The above differences are reflected in the much higher binding constant of TMalphaCD/(R)-(1) compared with that of TMbetaCD/(S)-(1) ( approximately 6800 and approximately 935 M(-1), respectively), determined by NMR in aqueous solution, and the ability of TMalphaCD to selectively precipitate (R)-(1) from racemic (1) in much higher yield than TMbetaCD precipitates (S)-(1).

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Section: Figurementioning

confidence: 94%

Section: Introductionmentioning

confidence: 99%

Non-covalent interactions in the crystallization of the enantiomers of 1,7-dioxaspiro[5.5]undecane (olive fly sex pheromone) by enantiospecific cyclodextrin hosts, hexakis(2,3,6-tri-O-methyl)-α-cyclodextrin and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin

Makedonopoulou

Yannakopoulou

Mentzafos

et al. 2001

Acta Crystallogr Sect B

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“…Only two hydrogen bonds of type CZH· · ·O were found (Table III); in one of these ðC5G2ZH· · ·O7Þ; the guest carbonyl O atom accepts a host methine H atom within the cavity, and in the other ðC13ZH· · ·O6G4Þ a guest furan H atom is donated to O6G4 on the primary side of a TRIMEB molecule translated along the x-axis. Several C6GnZH· · ·O5Gðn 2 1Þ hydrogen bonds [12,17] stabilise the observed conformation (Table III). A detailed comparison of the host conformation with that in the L-menthol complex [12] reveals remarkable similarities.…”

Section: Details Of Host Geometry and Guest Inclusion Modementioning

confidence: 86%

“…Significantly smaller ranges, reflecting a more 'round' host structure, were observed in, e.g. the TRIMEB· (S)-naproxen complex [17], namely 120.1 -139.08 (glycosidic oxygen angle), 4.64 -5.21 Å ðO4· · ·O4ðcentroidÞdistanceÞ; 4.25-4.54 Å ðglycosidic O4Gn· · ·O4Gðn þ 1ÞdistanceÞ and 9.4-44.38 (tilt angle magnitudes). The smaller deviation from 'roundness' is associated with insertion of the (S)-naproxen molecule with its molecular axis nearly parallel to that of the host and with a major portion of the guest protruding from the secondary side.…”

Section: Details Of Host Geometry and Guest Inclusion Modementioning

confidence: 96%

X-ray Structure and Thermal Properties of a 1:1 Inclusion Complex Between Permethylated β-Cyclodextrin and Psoralen

Caira

Giordano

Vilakazi

2004

Supramolecular Chemistry

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The phytoalexin psoralen (7H-furo [3,2-g ][1]benzopyran-7-one) has been included in heptakis(2,3,6-tri-O-methyl)-b-cyclodextrin (TRIMEB) to yield a solid crystalline complex of formula TRIMEBZpsoralenZH 2 O. Its X-ray structural elucidation provides an accurate model for cyclodextrin -furocoumarin interaction. Thermal analysis (hot stage microscopy, differential scanning calorimetry, thermogravimetry) indicated complex dehydration in the range 40 -1008C followed by melting at 137.18C. The X-ray analysis showed that the elongated guest molecule induces elliptical distortion in the host molecule, with which it interacts via CZH· · ·O hydrogen bonding and hydrophobic interactions. The host molecule adopts a very similar conformation to that in the isostructural complex with L-menthol as guest. Water molecules bridge symmetry-related TRIMEB molecules by hydrogen bonding.

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“…As a matter of fact, only a limited number of crystal structures of inclusion complexes of cyclodextrins with chiral guests are available in the Cambridge Structure DataBank (CSD), among which permethylated α-cyclodextrin binding S-and R-mandelic acid (CECMAY10 and CECMEC10, respectively) [11] or R-and S-isomers of flurbiprofen and S-ibuprofen (COYXAP10, COYXET20 [12] and RONWOG [13] respectively) included within the cavity of permethylated β-cyclodextrin. Selected examples of crystal structures of cyclodextrin's inclusion complexes with different chiral molecules are presented in Table S1 (supplementary material) [14][15][16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32].…”

Section: Introductionmentioning

confidence: 99%

Determination of the Absolute Configuration of Aegelinol by Crystallization of Its Inclusion Complex with β-Cyclodextrin

et al. 2012

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Abstract:The absolute configuration and structure of aegelinol, a pyranocoumarin isolated from Ferulago asparagifolia Boiss (Apiaceae), has been determined by crystallography. Crystal structure of the inclusion complex of aegelinol in β-cyclodextrin was determined (a = 15.404(1) Å, b = 15.281(1) Å, c = 17.890(1) Å, α = 99.662(1), β = 113.4230(1), γ = 102.481(1)°, P1; R 1 = 6.71%) and allowed unambiguous determination of the absolute configuration of the stereogenic center of aegelinol. The pyranocoumarin guest is included within the cylindrical cavity formed by dimeric β-cyclodextrin molecules with a head-to-head arrangement. Crystal structure of aegelinol alone was also determined (a = 6.8921(3) Å, b = 11.4302(9) Å, c = 44.964(3) Å, P2 1 2 1 2 1 ; R 1 = 4.44%) and allowed precise determination of its geometry. Aegelinol crystallizes with three molecules in the asymmetric unit held together by H-bonds and π-stacking interactions. OPEN ACCESSCrystals 2012, 2 1442

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X-ray structure and thermal analysis of a 1?1 complex between (S)-naproxen and heptakis(2,3,6-tri-O-methyl)-?-cyclodextrin

Cited by 28 publications

References 17 publications

Non-covalent interactions in the crystallization of the enantiomers of 1,7-dioxaspiro[5.5]undecane (olive fly sex pheromone) by enantiospecific cyclodextrin hosts, hexakis(2,3,6-tri-O-methyl)-α-cyclodextrin and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin

Non-covalent interactions in the crystallization of the enantiomers of 1,7-dioxaspiro[5.5]undecane (olive fly sex pheromone) by enantiospecific cyclodextrin hosts, hexakis(2,3,6-tri-O-methyl)-α-cyclodextrin and heptakis(2,3,6-tri-O-methyl)-β-cyclodextrin

X-ray Structure and Thermal Properties of a 1:1 Inclusion Complex Between Permethylated β-Cyclodextrin and Psoralen

Determination of the Absolute Configuration of Aegelinol by Crystallization of Its Inclusion Complex with β-Cyclodextrin

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