Cyclitol based metal complexing agents. Preference for the extraction of lithium by myo-inositol based crown-4-ethers depends on the relative orientation of crown ether oxygen atoms

Tetrahedron ◽  
2006 ◽  
Vol 62 (18) ◽  
pp. 4360-4363 ◽  
Author(s):  
Shailesh S. Dixit ◽  
Mysore S. Shashidhar ◽  
Subramanian Devaraj
1993 ◽  
Vol 48 (7) ◽  
pp. 893-897 ◽  
Author(s):  
Armand Blaschette ◽  
Karl-Heinz Nagel ◽  
Peter G. Jones

The complex [Na(15-crown-5)][N(SO2CH3)2] crystallizes at —25°C from a methanol solution containing equimolar amounts of NaN(SO2CH3)2 and 15-crown-S. Its crystallographic data at —95°C are: monoclinic, space group P 21/c, a = 852.1(5), b = 2731.9(12), c = 909.2(4) pm, β = 115.53(4)°, V = 1.910 nm3, Z = 4, Dx = 1.445 Mgm3. The structure in the solid state consists of ion pairs. The sodium cation is coordinated to the five oxygen atoms of the crown ether, one oxygen atom of the anion, and to the nitrogen atom of the anion. The bond distances are Na—O(crown) 238.7-247.2, Na—O(sulfonyl) 234.9, Na—N 275.8 pm. The sodium ion lies 78 pm out of the plane of the crown ether oxygen atoms. The conformation of the coronand is described.


1994 ◽  
Vol 49 (6) ◽  
pp. 852 ◽  
Author(s):  
Peter G. Jones ◽  
Oliver Hiemisch ◽  
Armand Blaschette

Single crystals of the title complex were fortuitously grown from a dichloromethane solution containing 18-crown-6 and sulfur trioxide. Crystallographic data (at -130 °C): triclinic, space group P1̄, a = 819.1(7). b = 860.6(7), c = 905.8(7) pm. a = 63.98(3), β = 66.56(3), y = 74.95(3)°, V = 0.5236 nm3, Z = 1, Dx, = 1.377 Mgm-3. In the centrosymmetric formula unit, the two CH2Cl2 molecules are situated one above and one below the plane of the ether oxygen atoms. They are C-H···O hydrogen-bonded to two opposing oxygen atoms (H-O 237.1 and 270.6 pm, C-O 335.5 and 365.9 pm, C-H···O 171.7 and 161.8°). The crown ether molecule has approximate D3d symmetry


Polyhedron ◽  
2010 ◽  
Vol 29 (11) ◽  
pp. 2269-2277 ◽  
Author(s):  
Lea Vaiana ◽  
Marta Mato-Iglesias ◽  
David Esteban-Gómez ◽  
Carlos Platas-Iglesias ◽  
Andrés de Blas ◽  
...  

1991 ◽  
Vol 69 (1) ◽  
pp. 12-19 ◽  
Author(s):  
Frank R. Fronczek ◽  
Richard D. Gandour ◽  
Thomas M. Fyles ◽  
Philippa J. Hocking ◽  
Susan J. McDermid ◽  
...  

The synthesis of crown ethers derived from meso-tartaric acid was investigated. The sodium salt of the bis(dimethylamide) of meso-tartaric acid reacted with diethylene glycol ditosylate to give a mixture of 18-crown-6 tetraamide and 27-crown-9 hexaamide crown ethers. The 2R,3S,11S,12R 18-crown-6 isomer crystallized in triclinic space group [Formula: see text] (a = 7.557(2), b = 8.866(2), c = 10.4133(13) Å, α = 94.13(2), β = 95.86(2), γ = 99.26(2)°, R = 0.040 for 2090 observed of 3129 unique reflections). The structures of the remaining products were then assigned from the NMR spectra. The solution conformations of the amide crown ethers were examined by NMR, and provide a rationale for the product distribution obtained. One of the 18-crown-6 isomers and a mixture of the two 27-crown-9 isomers were hydrolyzed to the respective crown ether carboxylic acids, and the stability constants for complexation of cations were determined by potentiometric titration. The meso tetra- and hexacarboxylates are remarkably nonselective and inefficient cation complexing agents, compared to related crown ethers from R,R-(+)-tartaric acid, due to the unfavorable conformational control exerted by the tartaro units. Key words: crown ether synthesis, complexation, crown ether conformation, meso-tartaric acid, crystal structure.


2009 ◽  
Vol 64 (3) ◽  
pp. 274-280 ◽  
Author(s):  
Qinghua Du ◽  
Dawei Song ◽  
Wansheng You ◽  
Yi Zhao ◽  
Tingting Gan ◽  
...  

A new crown ether-POM (POM = polyoxometalate) adduct with the molecular formula [(C14- H20O5)4(H3O)3]PMo12O40 ・ 0.5CH3CN (1) was isolated from the mixed solvent of acetonitrile and methanol. The adduct is constructed from Keggin [PMo12O40]3− anions and [(C14H20O5)- (H3O+)] and [(C14H20O5)2(H3O+)] cations via electrostatic and hydrogen bonding interactions. The supramolecular interactions combine the crown ether with oxonium ions. In the [(C14H20O5)- (H3O+)] moieties, the oxonium ions reside out of the planes defined by the oxygen atoms of the crown ether. The [(C14H20O5)2(H3O+)] moieties exhibit a sandwich structure. There exist hydrogen bonds between the oxonium ions of the [(C14H20O5)(H3O)]+ cations and the acetonitrile molecules and the terminal and bridging oxygen atoms of the [PMo12O40]3− anions. The adduct has been used as a bulk-modifier to fabricate a chemically modified carbon paste electrode (MCPE), which displays well-defined cyclic voltammograms with three reversible two-electron redox couples in acidic aqueous solution, and electrocatalytic activities towards the reduction of H2O2 and NO2−.


2008 ◽  
Vol 63 (9) ◽  
pp. 1101-1106
Author(s):  
Adelė Jonušaite ◽  
Arnold Adam

[Cs(18-crown-6)(CH3CO3)] (1) has been obtained by the reaction of CsOCH3 with 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane) in methanol in a CO2 atmosphere. The compound crystallizes in the monoclinic space group P21/n (no. 14) with a = 12.141(3), b = 8.610(1), c = 17.985(4) Å , β = 91.17(2)° and V = 1879.6(7) Å3. Cs is tenfold coordinated by six oxygen atoms of the crown ether and four oxygen atoms of two methyl carbonate anions which act as bidentate ligands. The slow hydrolysis of the methylcarbonate results in the hydrogencarbonate complex {Cs2(18-crown- 6)2 · [H2(CO3)2] · H2O · CH3OH} (2), the basic structural constitution of the starting material being retained. This new compound crystallizes in the monoclinic space group P21/c with a = 8.657 (7), b = 22.601 (2), c = 19.619 (15) Å, β = 92.09 (6)° and V = 3836.5 (6) Å3.


2004 ◽  
Vol 2 (4) ◽  
pp. 617-626 ◽  
Author(s):  
Mircho Georgiev ◽  
Tatiana Popova ◽  
Zhorro Nickolov ◽  
Nikolay Goutev ◽  
Georgi Georgiev ◽  
...  

AbstractThe hypothesis that the degree of hydration of poly(oxyethylene) (POE) in aqueous solution depends on the mole ratio of water molecules to ether oxygen atoms in the molecule has been verified by studying the isotropic Raman spectra in the O−H stretching region for four short-chain POEs (C 1EnC 1 withn=1−4). Excellent coincidence of the O−H stretching Raman band for all four POEs studied in the range of mole ratio H2O/Oether from 25 to 0.6 was observed, thus confirming the assumption stated above. A conclusion that all ether oxygen atoms in the POE molecule participate in hydrogen bonding with water molecules has been made.


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