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Structure, vibrational and electronic spectra, and bonding in trans-diaquabis(oxalato)vanadate(III) complex salts, A[V(ox)2(H2O)2]·xH2O (A = Cs, K, or NH3Me), and the X-ray crystal structure of the potassium salt (x= 3)

The X-ray crystal structure of potassium diaquabis(oxalato)vanadate(III), K[V(ox)₂(H₂0)2].3H₂0, has been determined [monoclinic, space group P2/c, with unit-cell parameters a = 7.971 (4), b = 5.691 (2), c = 14.167(5) A, β = 108.97(3)", and Z = 2]. The structure has been refined to an R value of...

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Main Authors: Stranger, Robert, Sirat, Kamaliah, Smith, Peter W.
Format: Article
Language:English
Published: Royal Society of Chemistry Publishing 1988
Online Access:http://psasir.upm.edu.my/id/eprint/34123/1/28.%2034123%20structure%20vibrational.pdf
http://psasir.upm.edu.my/id/eprint/34123/
http://pubs.rsc.org/en/Content/ArticleLanding/1988/DT/DT9880002245#!divAbstract
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spelling my.upm.eprints.341232015-04-24T00:52:06Z http://psasir.upm.edu.my/id/eprint/34123/ Structure, vibrational and electronic spectra, and bonding in trans-diaquabis(oxalato)vanadate(III) complex salts, A[V(ox)2(H2O)2]·xH2O (A = Cs, K, or NH3Me), and the X-ray crystal structure of the potassium salt (x= 3) Stranger, Robert Sirat, Kamaliah Smith, Peter W. The X-ray crystal structure of potassium diaquabis(oxalato)vanadate(III), K[V(ox)₂(H₂0)2].3H₂0, has been determined [monoclinic, space group P2/c, with unit-cell parameters a = 7.971 (4), b = 5.691 (2), c = 14.167(5) A, β = 108.97(3)", and Z = 2]. The structure has been refined to an R value of 0.032 using 560 independent reflections. In comparison with the corresponding Cs⁺ and NH₃Me⁺ salts, the K⁺ salt exhibits a significantly longer bond distance for axially co-ordinated water and this is manifested in band shifts of 500-1 000 cm ⁻¹ in the visible region. For all three salts vibrational spectra and single-crystal polarised electronic spectra are reported together with assignments. Analysis of the ligand-field spectra is presented in terms of the angular overlap model. It is shown that the band shifts occurring in the electronic spectrum of the K⁺ salt can be reproduced by a reduction in the cr-bonding capacity of the co-ordinated water together with a slight increase in the c bonding of the oxalate ligand, both of which areconsistent with structural differences existing between the K⁺ and the other two salts. Significant anisotropy exists in the metal- oxalate IT interaction with the in-plane contribution relatively small. In addition, anomalous temperature-dependent bands resulting from vibronic coupling with internal O-H stretching vibrations are present in the electronic spectra of both the Cs⁺and NH₂Me⁺ salts Royal Society of Chemistry Publishing 1988 Article NonPeerReviewed application/pdf en http://psasir.upm.edu.my/id/eprint/34123/1/28.%2034123%20structure%20vibrational.pdf Stranger, Robert and Sirat, Kamaliah and Smith, Peter W. (1988) Structure, vibrational and electronic spectra, and bonding in trans-diaquabis(oxalato)vanadate(III) complex salts, A[V(ox)2(H2O)2]·xH2O (A = Cs, K, or NH3Me), and the X-ray crystal structure of the potassium salt (x= 3). Journal of the Chemical Society, Dalton Transactions (9). pp. 2245-2253. ISSN 1472-7773; ESSN: 1364-5447 http://pubs.rsc.org/en/Content/ArticleLanding/1988/DT/DT9880002245#!divAbstract 10.1039/DT9880002245
institution Universiti Putra Malaysia
building UPM Library
collection Institutional Repository
continent Asia
country Malaysia
content_provider Universiti Putra Malaysia
content_source UPM Institutional Repository
url_provider http://psasir.upm.edu.my/
language English
description The X-ray crystal structure of potassium diaquabis(oxalato)vanadate(III), K[V(ox)₂(H₂0)2].3H₂0, has been determined [monoclinic, space group P2/c, with unit-cell parameters a = 7.971 (4), b = 5.691 (2), c = 14.167(5) A, β = 108.97(3)", and Z = 2]. The structure has been refined to an R value of 0.032 using 560 independent reflections. In comparison with the corresponding Cs⁺ and NH₃Me⁺ salts, the K⁺ salt exhibits a significantly longer bond distance for axially co-ordinated water and this is manifested in band shifts of 500-1 000 cm ⁻¹ in the visible region. For all three salts vibrational spectra and single-crystal polarised electronic spectra are reported together with assignments. Analysis of the ligand-field spectra is presented in terms of the angular overlap model. It is shown that the band shifts occurring in the electronic spectrum of the K⁺ salt can be reproduced by a reduction in the cr-bonding capacity of the co-ordinated water together with a slight increase in the c bonding of the oxalate ligand, both of which areconsistent with structural differences existing between the K⁺ and the other two salts. Significant anisotropy exists in the metal- oxalate IT interaction with the in-plane contribution relatively small. In addition, anomalous temperature-dependent bands resulting from vibronic coupling with internal O-H stretching vibrations are present in the electronic spectra of both the Cs⁺and NH₂Me⁺ salts
format Article
author Stranger, Robert
Sirat, Kamaliah
Smith, Peter W.
spellingShingle Stranger, Robert
Sirat, Kamaliah
Smith, Peter W.
Structure, vibrational and electronic spectra, and bonding in trans-diaquabis(oxalato)vanadate(III) complex salts, A[V(ox)2(H2O)2]·xH2O (A = Cs, K, or NH3Me), and the X-ray crystal structure of the potassium salt (x= 3)
author_facet Stranger, Robert
Sirat, Kamaliah
Smith, Peter W.
author_sort Stranger, Robert
title Structure, vibrational and electronic spectra, and bonding in trans-diaquabis(oxalato)vanadate(III) complex salts, A[V(ox)2(H2O)2]·xH2O (A = Cs, K, or NH3Me), and the X-ray crystal structure of the potassium salt (x= 3)
title_short Structure, vibrational and electronic spectra, and bonding in trans-diaquabis(oxalato)vanadate(III) complex salts, A[V(ox)2(H2O)2]·xH2O (A = Cs, K, or NH3Me), and the X-ray crystal structure of the potassium salt (x= 3)
title_full Structure, vibrational and electronic spectra, and bonding in trans-diaquabis(oxalato)vanadate(III) complex salts, A[V(ox)2(H2O)2]·xH2O (A = Cs, K, or NH3Me), and the X-ray crystal structure of the potassium salt (x= 3)
title_fullStr Structure, vibrational and electronic spectra, and bonding in trans-diaquabis(oxalato)vanadate(III) complex salts, A[V(ox)2(H2O)2]·xH2O (A = Cs, K, or NH3Me), and the X-ray crystal structure of the potassium salt (x= 3)
title_full_unstemmed Structure, vibrational and electronic spectra, and bonding in trans-diaquabis(oxalato)vanadate(III) complex salts, A[V(ox)2(H2O)2]·xH2O (A = Cs, K, or NH3Me), and the X-ray crystal structure of the potassium salt (x= 3)
title_sort structure, vibrational and electronic spectra, and bonding in trans-diaquabis(oxalato)vanadate(iii) complex salts, a[v(ox)2(h2o)2]·xh2o (a = cs, k, or nh3me), and the x-ray crystal structure of the potassium salt (x= 3)
publisher Royal Society of Chemistry Publishing
publishDate 1988
url http://psasir.upm.edu.my/id/eprint/34123/1/28.%2034123%20structure%20vibrational.pdf
http://psasir.upm.edu.my/id/eprint/34123/
http://pubs.rsc.org/en/Content/ArticleLanding/1988/DT/DT9880002245#!divAbstract
_version_ 1643831060192034816
score 13.211869

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