Hexakis(dimethylformamide)bis(hexaphenylcyclohexasiloxanehexaolato)hexacopper(II) Dimethylformamide Solvateстатья

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[1] Hexakis(dimethylformamide)bis(hexaphenylcyclohexasiloxanehexaolato)hexacopper(ii) dimethylformamide solvate / S. V. Lindeman, O. I. Shchegolikhina, Y. A. Molodtsova, A. A. Zhdanov // Acta Crystallographica Section C: Crystal Structure Communications. — 1997. — Vol. 53, no. 3. — P. 305–309. The sandwich-like title complex, hexakis(dimethylformamide)-1 kappa O,2 kappa O,3 kappa O,4 kappa O,5 kappa O,6 kappa O-bis[2,4,6,8,10,12-hexaphenylsiloxane-2, 4, 6, 8, 10, 12-hexaolato (6-)-1:2 kappa(2)O(1),2:3 kappa(2)O(2),3:4 kappa(2)O(3),4:5 kappa(2)O(4),5:6 kappa(2)O(6)]-hexacopper(II) tetrakis (dimethylformamide) solvate, [Cu-6(C3H7NO)(6){(C6H5)(6)O12Si6}(2)].4C(3)H(7)NO, is comprised of two regular crown-shaped macrocyclic hexadentate organosiloxanolate ligands chelating a flat Cu-6 hexagon, as in the ethanol-solvated analogue investigated previously. The title complex has a more distorted shape than the trigonal ethanol-solvated analogue, being slightly side-oblated, but still contains a large empty inner channel accessible by small molecules (the diameter of the free cross-section being about 2.5 Angstrom). Each Cu-II ion has a square-pyramidal coordination comprised of four basal siloxanolate O atoms and an apical dimethylformamide (DMFA) molecule (coordinated through its carbonyl group). The average bond lengths are Cu-O(Si) 1.964(11) and Cu-O(DMFA) 2.215(10) Angstrom. The structure contains four additional DMFA molecules per complex unit, linked by weak C-H ... O hydrogen bonds. Unexpectedly, the C=O bond length is longer [1.248(10) and 1.255(9) Angstrom] in the uncoordinated DMFA molecules than in the coordinated molecules [1.214-1.227(7) Angstrom]. [ DOI ]

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