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Two isostructural oxalato-bridged dimetallic heptanuclear [BaII3MIII4] complexes (M = Cr; Fe) associated with 3-aminopyridinium cations: Synthesis, crystal structure and magnetic properties

Two isostructural oxalato-bridged dimetallic heptanuclear [BaII3MIII4] complexes (M = Cr; Fe) associated with 3-aminopyridinium cations: Synthesis, crystal structure and magnetic properties
Two isostructural oxalato-bridged dimetallic heptanuclear [BaII3MIII4] complexes (M = Cr; Fe) associated with 3-aminopyridinium cations: Synthesis, crystal structure and magnetic properties

Two heterometallic heptanuclear oxalato-bridged [Ba II 3M III 4] complexes, (Org-H) 6[Ba 3(H 2O) 5.1Cr 4(C 2O 4) 12]·5H 2O (1) and (Org-H) 6[Ba 3(H 2O) 5.3Fe 4(C 2O 4) 12]·5H 2O (2) (Org-H = C 5H 7N 2 +: 3-aminopyridinium cation), have been synthesized through an ion-exchange reaction strategy by combining {Ba 6(H 2O) 17[M III(C 2O 4) 3] 4}·7H 2O (M = Cr; Fe) with (C 5H 7N 2) 2C 2O 4 in a 1:3 M ratio. They have been characterized by elemental and thermal analyses, IR spectroscopy, single-crystal X-ray diffraction and variable temperature magnetic susceptibility measurements. The hybrid salts 1 and 2 are isostructural and they crystallize in the monoclinic space group C2/c. Their structures consist of [Ba 3(H 2O) 5M 4(C 2O 4) 12] 6− dimetallic heptanuclear units (M = Cr, Fe), six 3-aminopyridinium cations and five crystallization water molecules. The d-metal atom is located in a distorted (2 + 2 + 2) octahedral environment of six O atoms from three chelating oxalato(2−) ligands. In the crystal, intermolecular N[sbnd]H⋯O and O[sbnd]H⋯O hydrogen bonds link the anions and 3-aminopyridinium cations and lattice water molecules into a three-dimensional framework. In addition, π-π stacking interactions [centroid-centroid distances of 3.680 to 3.938 Å] between the pyridine rings contribute to the stabilization of the framework. The magnetic properties of the two salts have been investigated and they revealed weak antiferromagnetic coupling between d-metal atoms.

Chromium(III), Heterometallic complexes, Iron(III), Magnetic properties, Oxalato(2−)
0277-5387
Choubeu, Coustel M. N.
91101021-654a-4a3f-a44d-cc716f4e8301
Ndosiri, Bridget N.
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Vezin, Hervé
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Minaud, Claire
a876f260-3a75-47a7-9556-cd3ca93b86ed
Orton, James
4e2a471f-9e11-4cb4-abb6-d0398047939f
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Nenwa, Justin
42cd6951-f090-4f24-9736-eb9351a94b67
Choubeu, Coustel M. N.
91101021-654a-4a3f-a44d-cc716f4e8301
Ndosiri, Bridget N.
bfd25af4-5d93-40b2-9ad1-7a351da5d3d4
Vezin, Hervé
82fdc1eb-a268-426e-97c2-6f115ea85ddf
Minaud, Claire
a876f260-3a75-47a7-9556-cd3ca93b86ed
Orton, James
4e2a471f-9e11-4cb4-abb6-d0398047939f
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Nenwa, Justin
42cd6951-f090-4f24-9736-eb9351a94b67

Choubeu, Coustel M. N., Ndosiri, Bridget N., Vezin, Hervé, Minaud, Claire, Orton, James, Coles, Simon J. and Nenwa, Justin (2021) Two isostructural oxalato-bridged dimetallic heptanuclear [BaII3MIII4] complexes (M = Cr; Fe) associated with 3-aminopyridinium cations: Synthesis, crystal structure and magnetic properties. Polyhedron, 193, [114885]. (doi:10.1016/j.poly.2020.114885).

Record type: Article

Abstract

Two heterometallic heptanuclear oxalato-bridged [Ba II 3M III 4] complexes, (Org-H) 6[Ba 3(H 2O) 5.1Cr 4(C 2O 4) 12]·5H 2O (1) and (Org-H) 6[Ba 3(H 2O) 5.3Fe 4(C 2O 4) 12]·5H 2O (2) (Org-H = C 5H 7N 2 +: 3-aminopyridinium cation), have been synthesized through an ion-exchange reaction strategy by combining {Ba 6(H 2O) 17[M III(C 2O 4) 3] 4}·7H 2O (M = Cr; Fe) with (C 5H 7N 2) 2C 2O 4 in a 1:3 M ratio. They have been characterized by elemental and thermal analyses, IR spectroscopy, single-crystal X-ray diffraction and variable temperature magnetic susceptibility measurements. The hybrid salts 1 and 2 are isostructural and they crystallize in the monoclinic space group C2/c. Their structures consist of [Ba 3(H 2O) 5M 4(C 2O 4) 12] 6− dimetallic heptanuclear units (M = Cr, Fe), six 3-aminopyridinium cations and five crystallization water molecules. The d-metal atom is located in a distorted (2 + 2 + 2) octahedral environment of six O atoms from three chelating oxalato(2−) ligands. In the crystal, intermolecular N[sbnd]H⋯O and O[sbnd]H⋯O hydrogen bonds link the anions and 3-aminopyridinium cations and lattice water molecules into a three-dimensional framework. In addition, π-π stacking interactions [centroid-centroid distances of 3.680 to 3.938 Å] between the pyridine rings contribute to the stabilization of the framework. The magnetic properties of the two salts have been investigated and they revealed weak antiferromagnetic coupling between d-metal atoms.

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Nenwa ACCEPTED MANUSCRIPT Polyhedron 2020 - Accepted Manuscript
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Accepted/In Press date: 27 October 2020
e-pub ahead of print date: 3 November 2020
Published date: 1 January 2021
Keywords: Chromium(III), Heterometallic complexes, Iron(III), Magnetic properties, Oxalato(2−)

Identifiers

Local EPrints ID: 445151
URI: http://eprints.soton.ac.uk/id/eprint/445151
ISSN: 0277-5387
PURE UUID: 462a0755-085b-4aad-8361-c768d8329453
ORCID for Simon J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 23 Nov 2020 17:31
Last modified: 15 Sep 2021 01:43

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Contributors

Author: Coustel M. N. Choubeu
Author: Bridget N. Ndosiri
Author: Hervé Vezin
Author: Claire Minaud
Author: James Orton
Author: Simon J. Coles ORCID iD
Author: Justin Nenwa

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