Crown Ether Complexation of Cationic Lanthanide(III) Chloride Species: Crystal and Molecular Structures of [DyCl2(H2O)2(12-crown-4)]-[SbCl 6].5THF (1), and [Er(12-crown-4)2(MeCN)][SbCl6]3 (2)

Gerald R. Willey; Marcus P. Spry; Timothy J. Woodman; Michael G.B. Drew

Crown Ether Complexation of Cationic Lanthanide(III) Chloride Species: Crystal and Molecular Structures of [DyCl₂(H₂O)₂(12-crown-4)]-[SbCl ₆].5THF (1), and [Er(12-crown-4)₂(MeCN)][SbCl₆]₃ (2)

Gerald R. Willey, Marcus P. Spry, Timothy J. Woodman, Michael G.B. Drew

Research output: Contribution to journal › Article › peer-review

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Abstract

Halide abstraction from a lanthanide(III) chloride using antimony(v) chloride as abstractor provides cationic metal species which can be stabilized in situ by crown ether complexation. The syntheses and structures of two such antimon(v)ate salts are presented. For [DyCl₂(12-crown-4)(H₂O)₂][SbCl ₆].5THF (1) the structure comprises independent [DyCl₂(12-crown-4)(H₂O)₂]⁺ cations and SbCl₆^- anions with lattice solvent (tetrahydrofuran) molecules. The cation structure has an approximate two-fold axis and the eight-coordinate metal environment can be considered as distorted square-antiprismatic. The Dy-O(crown) bond distances are equivalent 2.515(11) Å, the Dy-Cl bond distances are 2.631(5), 2.646(4) Å and the Dy-O(H₂O) bond distances are 2.364(10), 2.373(11) Å. In the case of [Er(12-crown-4)₂(MeCN)][SbCl₆]₃ (2) the independent nine-coordinate [Er(12-crown-4)₂(MeCN)]³⁺ cations show crystallographic C₂ symmetry with each metal centre being bonded to all four oxygen atoms of the two rings and to a nitrogen atom of a coordinated acetonitrile molecule. The Er-O(crown) bond lengths lie in the range 2.443(9)-2.503(9) Å, mean 2.463(9) Å and the Er-N bond length is 2.56(2) Å. The planes of the two oxa-crown rings intersect at an angle of 73.0(1)⁰.

Original language	English
Pages (from-to)	271-275
Number of pages	5
Journal	Journal of the Indian Chemical Society
Volume	75
Issue number	5
Publication status	Published - 31 May 1998

ASJC Scopus subject areas

Drug Discovery
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Electrochemistry

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Crown Ether Complexation of Cationic Lanthanide(III) Chloride Species: Crystal and Molecular Structures of [DyCl₂(H₂O)₂(12-crown-4)]-[SbCl ₆].5THF (1), and [Er(12-crown-4)₂(MeCN)][SbCl₆]₃ (2). / Willey, Gerald R.; Spry, Marcus P.; Woodman, Timothy J. et al.
In: Journal of the Indian Chemical Society, Vol. 75, No. 5, 31.05.1998, p. 271-275.

Research output: Contribution to journal › Article › peer-review

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title = "Crown Ether Complexation of Cationic Lanthanide(III) Chloride Species: Crystal and Molecular Structures of [DyCl2(H2O)2(12-crown-4)]-[SbCl 6].5THF (1), and [Er(12-crown-4)2(MeCN)][SbCl6]3 (2)",

abstract = "Halide abstraction from a lanthanide(III) chloride using antimony(v) chloride as abstractor provides cationic metal species which can be stabilized in situ by crown ether complexation. The syntheses and structures of two such antimon(v)ate salts are presented. For [DyCl2(12-crown-4)(H2O)2][SbCl 6].5THF (1) the structure comprises independent [DyCl2(12-crown-4)(H2O)2]+ cations and SbCl6- anions with lattice solvent (tetrahydrofuran) molecules. The cation structure has an approximate two-fold axis and the eight-coordinate metal environment can be considered as distorted square-antiprismatic. The Dy-O(crown) bond distances are equivalent 2.515(11) {\AA}, the Dy-Cl bond distances are 2.631(5), 2.646(4) {\AA} and the Dy-O(H2O) bond distances are 2.364(10), 2.373(11) {\AA}. In the case of [Er(12-crown-4)2(MeCN)][SbCl6]3 (2) the independent nine-coordinate [Er(12-crown-4)2(MeCN)]3+ cations show crystallographic C2 symmetry with each metal centre being bonded to all four oxygen atoms of the two rings and to a nitrogen atom of a coordinated acetonitrile molecule. The Er-O(crown) bond lengths lie in the range 2.443(9)-2.503(9) {\AA}, mean 2.463(9) {\AA} and the Er-N bond length is 2.56(2) {\AA}. The planes of the two oxa-crown rings intersect at an angle of 73.0(1)0.",

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T2 - Crystal and Molecular Structures of [DyCl2(H2O)2(12-crown-4)]-[SbCl 6].5THF (1), and [Er(12-crown-4)2(MeCN)][SbCl6]3 (2)

AU - Willey, Gerald R.

AU - Spry, Marcus P.

AU - Woodman, Timothy J.

AU - Drew, Michael G.B.

PY - 1998/5/31

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N2 - Halide abstraction from a lanthanide(III) chloride using antimony(v) chloride as abstractor provides cationic metal species which can be stabilized in situ by crown ether complexation. The syntheses and structures of two such antimon(v)ate salts are presented. For [DyCl2(12-crown-4)(H2O)2][SbCl 6].5THF (1) the structure comprises independent [DyCl2(12-crown-4)(H2O)2]+ cations and SbCl6- anions with lattice solvent (tetrahydrofuran) molecules. The cation structure has an approximate two-fold axis and the eight-coordinate metal environment can be considered as distorted square-antiprismatic. The Dy-O(crown) bond distances are equivalent 2.515(11) Å, the Dy-Cl bond distances are 2.631(5), 2.646(4) Å and the Dy-O(H2O) bond distances are 2.364(10), 2.373(11) Å. In the case of [Er(12-crown-4)2(MeCN)][SbCl6]3 (2) the independent nine-coordinate [Er(12-crown-4)2(MeCN)]3+ cations show crystallographic C2 symmetry with each metal centre being bonded to all four oxygen atoms of the two rings and to a nitrogen atom of a coordinated acetonitrile molecule. The Er-O(crown) bond lengths lie in the range 2.443(9)-2.503(9) Å, mean 2.463(9) Å and the Er-N bond length is 2.56(2) Å. The planes of the two oxa-crown rings intersect at an angle of 73.0(1)0.

AB - Halide abstraction from a lanthanide(III) chloride using antimony(v) chloride as abstractor provides cationic metal species which can be stabilized in situ by crown ether complexation. The syntheses and structures of two such antimon(v)ate salts are presented. For [DyCl2(12-crown-4)(H2O)2][SbCl 6].5THF (1) the structure comprises independent [DyCl2(12-crown-4)(H2O)2]+ cations and SbCl6- anions with lattice solvent (tetrahydrofuran) molecules. The cation structure has an approximate two-fold axis and the eight-coordinate metal environment can be considered as distorted square-antiprismatic. The Dy-O(crown) bond distances are equivalent 2.515(11) Å, the Dy-Cl bond distances are 2.631(5), 2.646(4) Å and the Dy-O(H2O) bond distances are 2.364(10), 2.373(11) Å. In the case of [Er(12-crown-4)2(MeCN)][SbCl6]3 (2) the independent nine-coordinate [Er(12-crown-4)2(MeCN)]3+ cations show crystallographic C2 symmetry with each metal centre being bonded to all four oxygen atoms of the two rings and to a nitrogen atom of a coordinated acetonitrile molecule. The Er-O(crown) bond lengths lie in the range 2.443(9)-2.503(9) Å, mean 2.463(9) Å and the Er-N bond length is 2.56(2) Å. The planes of the two oxa-crown rings intersect at an angle of 73.0(1)0.

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SN - 0019-4522

VL - 75

SP - 271

EP - 275

JO - Journal of the Indian Chemical Society

JF - Journal of the Indian Chemical Society

IS - 5

ER -

Crown Ether Complexation of Cationic Lanthanide(III) Chloride Species: Crystal and Molecular Structures of [DyCl₂(H₂O)₂(12-crown-4)]-[SbCl ₆].5THF (1), and [Er(12-crown-4)₂(MeCN)][SbCl₆]₃ (2)

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