Manganese(III) in a pseudo-compressed mixed-donor octahedral environment: Synthesis, X-ray crystal structure and physicochemical properties

Musa S. Shongwe, Sandy K. Vandayar, Manuel A. Fernandes, Helder M. Marques, Michael J. Morris, Sarah L. Heath

Research output: Contribution to journalArticle

6 Citations (Scopus)

Abstract

The compound [C5H10NH2][MnL2] [H2L = N-(2-hydroxynaphthalen-l-yl)sarcosine] has been synthesised and characterised using single-crystal X-ray crystallography, spectroscopy and magnetic susceptibility measurements. The crystallographic asymmetric unit displays two similar, independent [MnL2]- complex ions linked via piperidinium cations through hydrogen bonding. The complex ions are alternating and arranged in two non-interacting parallel chains. Each of the complex ions is six-co-ordinate with the donor atoms, provided by the two bifunctional tridentate sarcosinato ligands, being amine nitrogen atoms and carboxylate and naphtholate oxygen atoms. The anionic ligands are co-ordinated facially and are related by a crystallographic centre of inversion at the manganese ion. The mean bond distances Mn-Onaphtholate (1.885 Å), Mn-Ocarboxylate (2.069 Å) and Mn-Namine (2.198 Å) for the two molecules point to a pseudo-compressed octahedral geometry about the Mn(III) ion consistent with a pseudo-Jahn-Teller compression. IR spectroscopy corroborates the unidentate co-ordination fashion of the carboxylate group of the sarcosinato ligand and confirms the presence of the piperidinium cation. The room temperature effective magnetic moment, (8χT)1/2, is indicative of spin-only paramagnetism. As shown by the temperature dependence of the reciprocal of the magnetic susceptibility (χ-1), the magnetic behaviour of [C5H10NH2][MnL2] in the temperature range 5-300 K is in conformity with the Curie-Weiss law, χ = C/(T-θ), with θ = -0.12 K.

Original languageEnglish
Pages (from-to)2195-2201
Number of pages7
JournalPolyhedron
Volume20
Issue number17
DOIs
Publication statusPublished - Jul 15 2001

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Manganese
manganese
Crystal structure
X-Rays
Ions
magnetic permeability
X rays
crystal structure
synthesis
carboxylates
ligands
Ligands
ions
Magnetic susceptibility
x rays
Atoms
Temperature
Cations
Spectrum Analysis
cations

Keywords

  • Jahn-Teller distortion
  • Magnetic susceptibility
  • Manganese(III) complex
  • Spectroscopy
  • X-ray crystallography

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Manganese(III) in a pseudo-compressed mixed-donor octahedral environment : Synthesis, X-ray crystal structure and physicochemical properties. / Shongwe, Musa S.; Vandayar, Sandy K.; Fernandes, Manuel A.; Marques, Helder M.; Morris, Michael J.; Heath, Sarah L.

In: Polyhedron, Vol. 20, No. 17, 15.07.2001, p. 2195-2201.

Research output: Contribution to journalArticle

Shongwe, Musa S. ; Vandayar, Sandy K. ; Fernandes, Manuel A. ; Marques, Helder M. ; Morris, Michael J. ; Heath, Sarah L. / Manganese(III) in a pseudo-compressed mixed-donor octahedral environment : Synthesis, X-ray crystal structure and physicochemical properties. In: Polyhedron. 2001 ; Vol. 20, No. 17. pp. 2195-2201.
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abstract = "The compound [C5H10NH2][MnL2] [H2L = N-(2-hydroxynaphthalen-l-yl)sarcosine] has been synthesised and characterised using single-crystal X-ray crystallography, spectroscopy and magnetic susceptibility measurements. The crystallographic asymmetric unit displays two similar, independent [MnL2]- complex ions linked via piperidinium cations through hydrogen bonding. The complex ions are alternating and arranged in two non-interacting parallel chains. Each of the complex ions is six-co-ordinate with the donor atoms, provided by the two bifunctional tridentate sarcosinato ligands, being amine nitrogen atoms and carboxylate and naphtholate oxygen atoms. The anionic ligands are co-ordinated facially and are related by a crystallographic centre of inversion at the manganese ion. The mean bond distances Mn-Onaphtholate (1.885 {\AA}), Mn-Ocarboxylate (2.069 {\AA}) and Mn-Namine (2.198 {\AA}) for the two molecules point to a pseudo-compressed octahedral geometry about the Mn(III) ion consistent with a pseudo-Jahn-Teller compression. IR spectroscopy corroborates the unidentate co-ordination fashion of the carboxylate group of the sarcosinato ligand and confirms the presence of the piperidinium cation. The room temperature effective magnetic moment, (8χT)1/2, is indicative of spin-only paramagnetism. As shown by the temperature dependence of the reciprocal of the magnetic susceptibility (χ-1), the magnetic behaviour of [C5H10NH2][MnL2] in the temperature range 5-300 K is in conformity with the Curie-Weiss law, χ = C/(T-θ), with θ = -0.12 K.",
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AU - Shongwe, Musa S.

AU - Vandayar, Sandy K.

AU - Fernandes, Manuel A.

AU - Marques, Helder M.

AU - Morris, Michael J.

AU - Heath, Sarah L.

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N2 - The compound [C5H10NH2][MnL2] [H2L = N-(2-hydroxynaphthalen-l-yl)sarcosine] has been synthesised and characterised using single-crystal X-ray crystallography, spectroscopy and magnetic susceptibility measurements. The crystallographic asymmetric unit displays two similar, independent [MnL2]- complex ions linked via piperidinium cations through hydrogen bonding. The complex ions are alternating and arranged in two non-interacting parallel chains. Each of the complex ions is six-co-ordinate with the donor atoms, provided by the two bifunctional tridentate sarcosinato ligands, being amine nitrogen atoms and carboxylate and naphtholate oxygen atoms. The anionic ligands are co-ordinated facially and are related by a crystallographic centre of inversion at the manganese ion. The mean bond distances Mn-Onaphtholate (1.885 Å), Mn-Ocarboxylate (2.069 Å) and Mn-Namine (2.198 Å) for the two molecules point to a pseudo-compressed octahedral geometry about the Mn(III) ion consistent with a pseudo-Jahn-Teller compression. IR spectroscopy corroborates the unidentate co-ordination fashion of the carboxylate group of the sarcosinato ligand and confirms the presence of the piperidinium cation. The room temperature effective magnetic moment, (8χT)1/2, is indicative of spin-only paramagnetism. As shown by the temperature dependence of the reciprocal of the magnetic susceptibility (χ-1), the magnetic behaviour of [C5H10NH2][MnL2] in the temperature range 5-300 K is in conformity with the Curie-Weiss law, χ = C/(T-θ), with θ = -0.12 K.

AB - The compound [C5H10NH2][MnL2] [H2L = N-(2-hydroxynaphthalen-l-yl)sarcosine] has been synthesised and characterised using single-crystal X-ray crystallography, spectroscopy and magnetic susceptibility measurements. The crystallographic asymmetric unit displays two similar, independent [MnL2]- complex ions linked via piperidinium cations through hydrogen bonding. The complex ions are alternating and arranged in two non-interacting parallel chains. Each of the complex ions is six-co-ordinate with the donor atoms, provided by the two bifunctional tridentate sarcosinato ligands, being amine nitrogen atoms and carboxylate and naphtholate oxygen atoms. The anionic ligands are co-ordinated facially and are related by a crystallographic centre of inversion at the manganese ion. The mean bond distances Mn-Onaphtholate (1.885 Å), Mn-Ocarboxylate (2.069 Å) and Mn-Namine (2.198 Å) for the two molecules point to a pseudo-compressed octahedral geometry about the Mn(III) ion consistent with a pseudo-Jahn-Teller compression. IR spectroscopy corroborates the unidentate co-ordination fashion of the carboxylate group of the sarcosinato ligand and confirms the presence of the piperidinium cation. The room temperature effective magnetic moment, (8χT)1/2, is indicative of spin-only paramagnetism. As shown by the temperature dependence of the reciprocal of the magnetic susceptibility (χ-1), the magnetic behaviour of [C5H10NH2][MnL2] in the temperature range 5-300 K is in conformity with the Curie-Weiss law, χ = C/(T-θ), with θ = -0.12 K.

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KW - Spectroscopy

KW - X-ray crystallography

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