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Title: Crystal structures of complexes of the cys-syn-cys isomer of dicyclohexano-18-crown-6 with oxonium hexafluorotantalate and oxonium hexafluoroniobate

Abstract

The crystal structures of [(cys-syn-cys-dicyclohexano-18-crown-6 . H{sub 3}O)][TaF{sub 6}] and [(cys-syn-cys-dicyclohexano-18-crown-6 . H{sub 3}O)][NbF{sub 6}] complex compounds are determined using X-ray diffraction analysis. The tantalum complex has two polymorphic modifications, namely, the monoclinic (I) and triclinic (II) modifications. The unit cell parameters of these compounds are as follows: a = 8.507(4) A, b = 11.947(5) A, c = 27.392(12) A, {beta} = 93.11(1) deg., Z = 4, and space group P2{sub 1}/n for modification I; and a = 10.828(1) A, b = 11.204(1) A, c = 12.378(1) A, {alpha} = 72.12(1) deg., {beta} = 79.40(1) deg., {gamma} = 73.70(1) deg., Z = 2, and space group P-1 for modification II. The triclinic niobium complex [(cys-syn-cys-dicyclohexano-18-crown-6 . H{sub 3}O)][NbF{sub 6}] (III) with the unit cell parameters a = 10.796(3) A, b = 11.183(3) A, c = 12.352(3) A, {alpha} = 72.364(5) deg., {beta} = 79.577(5) deg., {gamma} = 73.773(4) deg., Z = 2, and space group P-1 is isostructural with tantalum complex II. The structures of all three complexes are ionic in character. The oxonium cation in complexes I-III is encapsulated by the crown ether and thus forms one ordinary and two bifurcated hydrogen bonds with the oxygen atoms of themore » crown ether. This macrocyclic cation is bound to the anions through the C-H...F contacts (H...F, 2.48-2.58 A). The conformation of the macrocycle in complex I differs substantially from that in complex II (III)« less

Authors:
 [1]; ;  [2];  [3]; ;  [4];  [5];  [6];  [7]
  1. Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of), E-mail: fonari.xray@phys.asm.md
  2. Russian Academy of Sciences, Shubnikov Institute of Crystallography (Russian Federation), E-mail: furm@ns.crys.ras.ru
  3. Russian Academy of Sciences, Nesmeyanov Institute of Organoelement Compounds (Russian Federation)
  4. Tamkang University, Department of Chemistry (China)
  5. Ministry of Education and Science and National Academy of Sciences of Ukraine, Odessa State Environmental University (Ukraine), E-mail: edganin@yahoo.com
  6. Academy of Sciences of Ukraine, Physicochemical Institute for Human and Environmental Protection, Ministry of Education and Science and National (Ukraine), E-mail: eksvar@ukr.net
  7. Academy of Sciences of Moldova, Institute of Applied Physics (Moldova, Republic of)
Publication Date:
OSTI Identifier:
21090946
Resource Type:
Journal Article
Resource Relation:
Journal Name: Crystallography Reports; Journal Volume: 52; Journal Issue: 2; Other Information: DOI: 10.1134/S1063774507020150; Copyright (c) 2007 Nauka/Interperiodica; Article Copyright (c) 2007 Pleiades Publishing, Inc; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; CROWN ETHERS; ISOMERS; MONOCLINIC LATTICES; NIOBIUM COMPLEXES; SPACE GROUPS; TANTALUM COMPLEXES; X-RAY DIFFRACTION

Citation Formats

Fonari, M. S., Alekseeva, O. A., Furmanova, N. G., Lysenko, K. A., Wang, Wen-Jwu, Tang, Shang-Wei, Ganin, E. V., Gel'mbol'dt, V. O., and Simonov, Yu. A. Crystal structures of complexes of the cys-syn-cys isomer of dicyclohexano-18-crown-6 with oxonium hexafluorotantalate and oxonium hexafluoroniobate. United States: N. p., 2007. Web. doi:10.1134/S1063774507020150.
Fonari, M. S., Alekseeva, O. A., Furmanova, N. G., Lysenko, K. A., Wang, Wen-Jwu, Tang, Shang-Wei, Ganin, E. V., Gel'mbol'dt, V. O., & Simonov, Yu. A. Crystal structures of complexes of the cys-syn-cys isomer of dicyclohexano-18-crown-6 with oxonium hexafluorotantalate and oxonium hexafluoroniobate. United States. doi:10.1134/S1063774507020150.
Fonari, M. S., Alekseeva, O. A., Furmanova, N. G., Lysenko, K. A., Wang, Wen-Jwu, Tang, Shang-Wei, Ganin, E. V., Gel'mbol'dt, V. O., and Simonov, Yu. A. Thu . "Crystal structures of complexes of the cys-syn-cys isomer of dicyclohexano-18-crown-6 with oxonium hexafluorotantalate and oxonium hexafluoroniobate". United States. doi:10.1134/S1063774507020150.
@article{osti_21090946,
title = {Crystal structures of complexes of the cys-syn-cys isomer of dicyclohexano-18-crown-6 with oxonium hexafluorotantalate and oxonium hexafluoroniobate},
author = {Fonari, M. S. and Alekseeva, O. A. and Furmanova, N. G. and Lysenko, K. A. and Wang, Wen-Jwu and Tang, Shang-Wei and Ganin, E. V. and Gel'mbol'dt, V. O. and Simonov, Yu. A.},
abstractNote = {The crystal structures of [(cys-syn-cys-dicyclohexano-18-crown-6 . H{sub 3}O)][TaF{sub 6}] and [(cys-syn-cys-dicyclohexano-18-crown-6 . H{sub 3}O)][NbF{sub 6}] complex compounds are determined using X-ray diffraction analysis. The tantalum complex has two polymorphic modifications, namely, the monoclinic (I) and triclinic (II) modifications. The unit cell parameters of these compounds are as follows: a = 8.507(4) A, b = 11.947(5) A, c = 27.392(12) A, {beta} = 93.11(1) deg., Z = 4, and space group P2{sub 1}/n for modification I; and a = 10.828(1) A, b = 11.204(1) A, c = 12.378(1) A, {alpha} = 72.12(1) deg., {beta} = 79.40(1) deg., {gamma} = 73.70(1) deg., Z = 2, and space group P-1 for modification II. The triclinic niobium complex [(cys-syn-cys-dicyclohexano-18-crown-6 . H{sub 3}O)][NbF{sub 6}] (III) with the unit cell parameters a = 10.796(3) A, b = 11.183(3) A, c = 12.352(3) A, {alpha} = 72.364(5) deg., {beta} = 79.577(5) deg., {gamma} = 73.773(4) deg., Z = 2, and space group P-1 is isostructural with tantalum complex II. The structures of all three complexes are ionic in character. The oxonium cation in complexes I-III is encapsulated by the crown ether and thus forms one ordinary and two bifurcated hydrogen bonds with the oxygen atoms of the crown ether. This macrocyclic cation is bound to the anions through the C-H...F contacts (H...F, 2.48-2.58 A). The conformation of the macrocycle in complex I differs substantially from that in complex II (III)},
doi = {10.1134/S1063774507020150},
journal = {Crystallography Reports},
number = 2,
volume = 52,
place = {United States},
year = {Thu Mar 15 00:00:00 EDT 2007},
month = {Thu Mar 15 00:00:00 EDT 2007}
}
  • The crystal structures of [(benzo-18-crown-6) . H{sub 3}O]TaF{sub 6} and [(benzo-18-crown-6) . H{sub 3}O]NbF{sub 6} complex compounds are determined by X-ray diffraction. It is revealed that the tantalum complex has two polymorphic modifications, namely, the monoclinic (I) and orthorhombic (II) modifications. The unit cell parameters of these compounds are as follows: a = 14.784(2) A, b = 8.390(4) A, c = 18.005(6) A, {beta} = 95.78(2) deg., Z = 4, and space group P2{sub 1}/n for modification I; and a = 8.456(2) A, b = 21.967(5) A, c = 24.122(5) A, Z = 8, and space group Pbca for modificationmore » II. The orthorhombic niobium complex [(benzo-18-crown-6) . H{sub 3}O]NbF{sub 6} with the unit cell parameters a = 8.454(1) A, b = 21.943(3) A, c = 24.127(4) A, Z = 8, and space group Pbca (III) is isostructural with tantalum complex II. The oxonium cation in complexes I-III is encapsulated by the crown ether and thus forms one ordinary and two bifurcate hydrogen bonds with the oxygen atoms of the crown ether. This macrocyclic cation is bound to the anions through the C-H ...F contacts (H...F, 2.48-2.58 A)« less
  • Two isostructural complexes of dioxonium [H{sub 5}O{sub 2}]{sup +} with tetrabenzo-30-crown-10 of the compositions [(tetrabenzo-30-crown-10 . H{sub 5}O{sub 2})][TaF{sub 6}] (I) and [(tetrabenzo-30-crown-10 . H{sub 5}O{sub 2})][NbF{sub 6}] (II) are studied using X-ray diffraction. The complexes crystallize in the monoclinic crystal system (space group C2/c, Z = 4). The unit cell parameters of these compounds are as follows: a = 15.6583(12) A, b = 15.2259(13) A, c = 16.4473(13) A, and {beta} = 99.398(6) deg. for complex I and a = 15.7117(12) A, b = 15.2785(15) A, c = 16.5247(15) A, and {beta} = 99.398(7) deg. for complex II. Thesemore » complexes belong to the ionic type. The dioxonium cation [H{sub 5}O{sub 2}]{sup +} in the form of the two-unit cluster [H{sub 3}O . H{sub 2}O]{sup +} is stabilized by the strong hydrogen bond OH-O [O-O, 2.353(4) A] and encapsulated by the crown ether. Each oxygen atom of the dioxonium cation also forms two oxygen bonds O-O(crown). The crown ether adopts an unusual two-level (pocket-like) conformation, which provides a complete encapsulation of the oxonium associate. The interaction of the cationic complex with the anion in the crystal occurs through contacts of the C-H-F type.« less
  • Two isostructural complexes of dioxonium [H{sub 5}O{sub 2}]{sup +} with tetrabenzo-30-crown-10 of the compositions [(tetrabenzo-30-crown-10 {center_dot} H{sub 5}O{sub 2})][TaF{sub 6}] (I) and [(tetrabenzo-30-crown-10 {center_dot} H{sub 5}O{sub 2})][NbF{sub 6}] (II) are studied using X-ray diffraction. The complexes crystallize in the monoclinic crystal system (space group C2/c, Z = 4). The unit cell parameters of these compounds are as follows: a = 15.6583(12) Angstrom-Sign , b = 15.2259(13) Angstrom-Sign , c = 16.4473(13) Angstrom-Sign , and {beta} = 99.398(6) Degree-Sign for complex I and a = 15.7117(12) Angstrom-Sign , b = 15.2785(15) Angstrom-Sign , c = 16.5247(15) Angstrom-Sign , and {beta} =more » 99.398(7) Degree-Sign for complex II. These complexes belong to the ionic type. The dioxonium cation [H{sub 5}O{sub 2}]{sup +} in the form of the two-unit cluster [H{sub 3}O {center_dot} H{sub 2}O]{sup +} is stabilized by the strong hydrogen bond OH Midline-Horizontal-Ellipsis O [O Midline-Horizontal-Ellipsis O, 2.353(4) Angstrom-Sign ] and encapsulated by the crown ether. Each oxygen atom of the dioxonium cation also forms two oxygen bonds O Midline-Horizontal-Ellipsis O(crown). The crown ether adopts an unusual two-level (pocket-like) conformation, which provides a complete encapsulation of the oxonium associate. The interaction of the cationic complex with the anion in the crystal occurs through contacts of the C-H Midline-Horizontal-Ellipsis F type.« less
  • The far-IR spectra for NH/sub 4//sup +/ and H/sub 3/O/sup +/ complexes with 18-crown-6 have been obtained and the hydrogen-bond vibrational mode ..nu../sub sigma/ has been assigned. These results illustrate the suitability of far-IR spectroscopy for exploring crown ether molecular ion interactions.
  • As a part of the study of hazardous metal ion separations, the extraction of Sr{sup 2+} and Pb{sup 2+} from solutions containing nitric acid and various nitrate salts has been investigated. High partition ratios (D{sub Sr} > 100-10) were observed using comparatively low (10--50mM) concentrations of dicyclohexano-18-crown-6 in a group of nitrile solvents with relatively high dielectric constants (adiponitrile, glutaronitrile, succinonitrile, malononitrile; {var_epsilon} = 30--60) which are able to participate in coalescence extraction. Equilibria in the solvent extraction system were characterized, with Sr(II) and Pb(II) occurring in the organic phase primarily as partially dissociated ion pairs. A dramatic increase ofmore » extraction efficiency over traditional systems is achieved because of the formation of solvated cationic complexes in the organic phase.« less