Complexes of 18-crown-6 macrocyclic ethers obtained from ethereal solvents. Complexes of potassium and sodium salts with host:guest ratios of 1:2 and 1:3

Rodrigue, André; Bovenkamp, John W.; Lacroix, Benoit V.; Bannard, R. A. B.; Buchanan, G. W.

doi:10.1139/v86-133

Cited by 15 publications

(9 citation statements)

References 16 publications

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“…Work is underway to obtain crystal structures of these complexes. A similar situation was observed for the 1:2 and 1:3 host:guest complexes of sodium and potassium phenoxide with 18-crown-6 and its derivatives (21). The A , , , value of dicyclohexano-18-crown-6(isomer A) -2NaOPh in dimethoxyethane was identical to the value obtained for NaOPh itself (21), indicating that the macrocycle very likely was complexed to an aggregate of NaOPh.…”

Section: Crystal Structures Of 15-crown-52lioph ( I a And I B)supporting

confidence: 76%

“…A similar situation was observed for the 1:2 and 1:3 host:guest complexes of sodium and potassium phenoxide with 18-crown-6 and its derivatives (21). The A , , , value of dicyclohexano-18-crown-6(isomer A) -2NaOPh in dimethoxyethane was identical to the value obtained for NaOPh itself (21), indicating that the macrocycle very likely was complexed to an aggregate of NaOPh. The crystal structure of dicyclohexano-18-crown-6(isomer A).2NaOPh (22) confirmed this and showed two macrocycles complexed to an aggregate of four NaOPh molecules.…”

Section: Crystal Structures Of 15-crown-52lioph ( I a And I B)supporting

confidence: 76%

“…The complexation of a cation by a macrocycle and the stoichiometry of the resulting macrocycle salt complex are dependent upon a number of factors; including (i) compatibility of cavity size and cation diameter, (ii) anion effects, and (iii) solvent effects (2)(3)(4)(5)(6)(7)(8)(9). Recently, Rodrigue et al (21) demonstrated the importance of solvent effects in the formation of 18-crown-6 macrocycle salt complexes. Using ethereal solvents such as 1 ,Zdimethoxyethane, tetrahydrofuran, and diethyl ether, complexes were isolated which exhibited novel macrocyc1e:salt ratios of 1:2 and 1:3; e.g.…”

Section: Introductionmentioning

confidence: 99%

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Complexes of 15-crown-5 and cyclohexano-15-crown-5 with lithium, sodium, and potassium phenoxide having macrocycle: salt ratios of 1:1 and 1:2. The crystal structures of two polymorphs of 15-crown-5•2LiOPh

Murchie¹,

Bovenkamp²,

Rodrigue³

et al. 1988

Can. J. Chem.

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Chem. 66, 2515 (1988).The syntheses, in ethereal solvents, of the complexes of 15-crown-5 and cyclohexano-15-crown-5 with lithium, sodium, and potassium phenoxide are described. The two macrocycles form complexes with lithium and sodium phenoxide with host:guest ratios of 1:2. Potassium phenoxide, however, was complexed by the two macrocycles to give products with macrocycle:salt ratios of 1:l. Crystals of 15-crown-5.2LiOPh were obtained for X-ray diffraction structure determinations. In fact, the crystal structures of tw_o co-crystallizing polymorphs of this complex ( l a and Jb) have been determined. Polymorph l a crystallizes in space group P 1 with a = 11.386(4), b = 11.901(4), c = 10.654(4)A, a = 106.53(3), P = 112.60(3), y = 106.52(3)", and Z = 2. Polymorph l b crystallizes in space group P2'/n with a = 15.355(4), b = 11.642(2), c = 13.595(6) A, P = 104.56(3)", and Z = 4. Both structures were solved by direct methods, and refined by full-matrix least-squares calculations to residuals, R, of 0.053 and 0.055 for polymorphs l a and l b , respectively. The structures of the two polymorphs differ only in the orientation of the phenoxides. The structures show a dimer, (15-~rown-5.2LiOPh)~, which consists of an aggregate of four lithium phenoxide molecules complexed by two 15-crown-5 macrocycles. The two lithiums of each monomeric unit of this dimer have different crystallographic and chemical environments. One lithium is coordinated to all five oxygens of the macrocycle and to one of the phenoxide oxygens while the other lithium is coordinated to only one oxygenof the macrocycle and to three phenoxide oxygens. [Traduit par la revue] Introduction In 1967, Pedersen (I) showed that crown ethers form stable complexes with alkali metal salts. Since then, crown ether complexes have been extensively studied. Several reviews (2-9) have been written on this topic. A large number of alkali

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Section: Crystal Structures Of 15-crown-52lioph ( I a And I B)supporting

confidence: 76%

Section: Crystal Structures Of 15-crown-52lioph ( I a And I B)supporting

confidence: 76%

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Complexes of 15-crown-5 and cyclohexano-15-crown-5 with lithium, sodium, and potassium phenoxide having macrocycle: salt ratios of 1:1 and 1:2. The crystal structures of two polymorphs of 15-crown-5•2LiOPh

Murchie¹,

Bovenkamp²,

Rodrigue³

et al. 1988

Can. J. Chem.

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“…I host:guest complex of sodium phenoxide with DC-18-crown-6 (isomer A) was obtained from ethereal solvents (12). It was clear that, in both cases, the nature of the solvent used and the 1 nature of the counterion played a role in the unusual host:guest i ratios.…”

Section: Introductionmentioning

confidence: 99%

“…The synthetic method used for the preparation of the two complexes has been described in a previous publication (12). Suitable crystals of DC-18-crown-6 (isomer A).2NaOPh were obtained by dissolving the complex in dry tetrahydrofuran in a Dri-Lab (Vacuum Atmospheres) under an argon atmosphere and allowing the solvent to evaporate completely at room temperature.…”

Section: Introductionmentioning

confidence: 99%

The crystal structures of the 1:2 host:guest complexes of dicyclohexano-18-crown-6 (isomers A and B) with sodium and potassium phenoxide

Fraser¹,

Fortier²,

Rodrigue³

et al. 1986

Can. J. Chem.

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. Can. J. Chem. 64, 816 (1986). The crystal structures of the 1 :2 host:guest complexes of dicyclohexano-18-crown-6 (isomer B) with potassium phenoxide and dicyclohexano-18-crown-6 (isomer A) with sodium phenoxide have been determined. The potassium phenoxide complex crystallizes in space group PI with a = 10.023(2), b = 11.238(2), c = 7.546(2) A, cx = 95.73(2), P = 103.04(2), y = 92.03(2)", and Z = 1. The sodiumphenoxide complex crystallizes in space group P2,/n with a = 19.185(12), b = 13.266(5), c = 13.038(5) A, P = 96.55(4)", and Z = 4. Both structures were solved by direct methods and refined by full matrix least-squares calculations to a residual, R , of 0.035. The host conformation as well as the metal cation coordination differ considerably in the two structures. In the potassium phenoxide complex, the two cations are related by symmetry and have, consequently, the same chemical environment. Each potassium is located approximately halfway between the plane formed by the crown ether oxygens and the phenoxide anions and is coordinated to four of the crown oxygens and to two phenoxide oxygens. The oxygens of the crown are found to outline an elliptical cavity and to lie approximately in a plane. In the sodium phenoxide complex, the two sodiums have different crystallographic and chemical environments. One sodium is coordinated to the six hexaether oxygens, withdistances ranging from 2.36 to 2.84 A, and to one of the phenoxide oxygens. The other sodium is coordinated to only one of the crown oxygens and to three of the phenoxide oxygens. The hexaether adopts a highly irregular conformation. affinCes par la mtthode des moindres carrts (matrice entiere) jusqu'a des valeurs rCsiduelles de R de 0,035. La conformation de la molCcule hate ainsi que la coordination du cation mitallique different considtrablement dans les deux structures. Dans le complexe du phknolate de potassium, les deux cations sont relits par de la symttrie et ont donc des environnements chimiques semblables. Chaque potassium est situt approximativement a mi-chemin entre le plan form6 par les oxygknes de la couronne et celui des anions phtnolates et chacun est coordonnk a quatre oxygknes de la couronne et a deux oxygknes des phenolates. On a trouvC que les oxygknes de la couronne foment le contour d'une cavitt ellipsoidale et qu'ils se retrouvent approximativement dans un plan. Dans le complexe du phCnolate de sodium, les deux cations de sodium se trouvent dans des environnements cristallographiques ainsi que chimiques qui sont difftrents. Un des cations de sodium est coordonnC aux six oxygknes de l'tther, avec des distances variant de 2,36 a 2,84 A, et a l'un des oxygknes des phenolates. L'autre sodium est coordonnt a un seul des oxygknes de la couronne et a trois oxygtnes des phCnolates. La conformation de la couronne est hautement irrtguliere.[Traduit par la revue] Introduction .Of the crown ethers, 18-crown-6 is probably the most extensively characterized. Nuclear magnetic resonance (nrnr), infrared (ir), X-ray diffraction studies, as well ...

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Di‐Benzo‐18‐Crown‐6 and its Derivatives as Ligands in the Search for Ion Channels

Fromm

Bergougnant²,

Robin³

2006

Zeitschrift anorg allge chemie

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Abstract. Based on the previously reported one-dimensional chan-, which is realized by stacking of crown ether molecules (DB18C6 ϭ dibenzo-18-crown-6), other synthetic approaches towards ionic channels and their results are presented in this paper. The "cutting out" approach using DB18C6 as scissor, applied on NaI, yields the compound [Naʚ(DB18C6)I(THF)]-[Naʚ(DB18C6)(H 2 O) 2 ]I(THF) 2 (CHI 3 ) (1), in high yield. It is based on a neutral and a cationic complex of sodium by DB18C6 linked via H-bonding to give short chain fragments. The anion exchange approach, trying to replace I 3 Ϫ by Br 3 Ϫ leads to the intercalation

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Complexes of 18-crown-6 macrocyclic ethers obtained from ethereal solvents. Complexes of potassium and sodium salts with host:guest ratios of 1:2 and 1:3

Cited by 15 publications

References 16 publications

Complexes of 15-crown-5 and cyclohexano-15-crown-5 with lithium, sodium, and potassium phenoxide having macrocycle: salt ratios of 1:1 and 1:2. The crystal structures of two polymorphs of 15-crown-5•2LiOPh

Complexes of 15-crown-5 and cyclohexano-15-crown-5 with lithium, sodium, and potassium phenoxide having macrocycle: salt ratios of 1:1 and 1:2. The crystal structures of two polymorphs of 15-crown-5•2LiOPh

The crystal structures of the 1:2 host:guest complexes of dicyclohexano-18-crown-6 (isomers A and B) with sodium and potassium phenoxide

Di‐Benzo‐18‐Crown‐6 and its Derivatives as Ligands in the Search for Ion Channels

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