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−)
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
1 January 2021
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).
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.
Text
Nenwa ACCEPTED MANUSCRIPT Polyhedron 2020
- Accepted Manuscript
More information
Accepted/In Press date: 27 October 2020
e-pub ahead of print date: 3 November 2020
Published date: 1 January 2021
Additional Information:
Funding Information:
We are indebted to Prof. Augustin Ephraim Nkengfack (Organic Chemistry Department, University of Yaounde I, Cameroon) for the donation of organic reagents. We would like to thank the Engineering and Physical Sciences Research Council for funding the UK National Crystallography Service.
Publisher Copyright:
© 2020 Elsevier Ltd
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
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Date deposited: 23 Nov 2020 17:31
Last modified: 17 Mar 2024 06:04
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Contributors
Author:
Coustel M. N. Choubeu
Author:
Bridget N. Ndosiri
Author:
Hervé Vezin
Author:
Claire Minaud
Author:
James Orton
Author:
Justin Nenwa
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