Tris(oxalato)chromate(III) hybrid salts templated by pyridinium and mixed pyridinium-ammonium cations: synthesis, structures and magnetism
Tris(oxalato)chromate(III) hybrid salts templated by pyridinium and mixed pyridinium-ammonium cations: synthesis, structures and magnetism
By modifying the stoichiometric ratio of starting materials, two tris(oxalato)chromate(III) salts, (C7H11N2)3[Cr(C2O4)3] (1) and (C5H8N3)2(NH4)[Cr(C2O4)3]·2H2O (2) {(C7H11N2)+ = 2-amino-4,6-dimethylpyridinium, (C5H8N3)+ = 2,6-diaminopyridinium}, were synthesized and characterized by elemental and thermal analyses, single-crystal X-ray diffraction, IR and UV − Vis spectroscopies, EPR and SQUID measurements. Salt 1 exhibits a 3-D supramolecular framework based on [Cr(C2O4)3]3- and 2-amino-4,6-dimethylpyridinim cations, (C7H11N2)+, via N–H···O hydrogen bonds. Interestingly, π–π stacking interactions between pyridine rings contribute to the stabilization of the crystal packing. In contrast to salt 1, no π–π stacking interactions are observed in the mixed-cation salt 2 and its crystal packing is consolidated by N–H···O and O − H···O hydrogen bonds. EPR spectra of 1 and 2 are consistent with the oxidation state +3 of the chromium center in an octahedral environment. Temperature-dependence of the magnetic susceptibility data investigated from 2 to 300 K revealed the existence of zero-field splitting effects (ZFS) for Cr(III) ions in both compounds.
crystal structures, Hybrid salts, magnetism, oxalate chromium(III) complex, stoichiometry
1209-1221
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 B.
4e2a471f-9e11-4cb4-abb6-d0398047939f
Coles, Simon J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Nenwa, Justin
42cd6951-f090-4f24-9736-eb9351a94b67
1 March 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 B.
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 B., Coles, Simon J. and Nenwa, Justin
(2021)
Tris(oxalato)chromate(III) hybrid salts templated by pyridinium and mixed pyridinium-ammonium cations: synthesis, structures and magnetism.
Journal of Coordination Chemistry, 74 (8), .
(doi:10.1080/00958972.2021.1890048).
Abstract
By modifying the stoichiometric ratio of starting materials, two tris(oxalato)chromate(III) salts, (C7H11N2)3[Cr(C2O4)3] (1) and (C5H8N3)2(NH4)[Cr(C2O4)3]·2H2O (2) {(C7H11N2)+ = 2-amino-4,6-dimethylpyridinium, (C5H8N3)+ = 2,6-diaminopyridinium}, were synthesized and characterized by elemental and thermal analyses, single-crystal X-ray diffraction, IR and UV − Vis spectroscopies, EPR and SQUID measurements. Salt 1 exhibits a 3-D supramolecular framework based on [Cr(C2O4)3]3- and 2-amino-4,6-dimethylpyridinim cations, (C7H11N2)+, via N–H···O hydrogen bonds. Interestingly, π–π stacking interactions between pyridine rings contribute to the stabilization of the crystal packing. In contrast to salt 1, no π–π stacking interactions are observed in the mixed-cation salt 2 and its crystal packing is consolidated by N–H···O and O − H···O hydrogen bonds. EPR spectra of 1 and 2 are consistent with the oxidation state +3 of the chromium center in an octahedral environment. Temperature-dependence of the magnetic susceptibility data investigated from 2 to 300 K revealed the existence of zero-field splitting effects (ZFS) for Cr(III) ions in both compounds.
Text
Tris(oxaloto)_CordChem
- Accepted Manuscript
More information
Accepted/In Press date: 27 December 2020
e-pub ahead of print date: 1 March 2021
Published date: 1 March 2021
Additional Information:
Funding Information:
This work was financially supported by the UK Engineering and Physical Sciences Council funding for the UK National Crystallography Service. The authors thank Prof. Augustin Ephraim Nkengfack (Organic Chemistry Department, University of Yaounde I, Cameroon) for the donation of organic reagents.
Publisher Copyright:
© 2021 Informa UK Limited, trading as Taylor & Francis Group.
Copyright:
Copyright 2021 Elsevier B.V., All rights reserved.
Keywords:
crystal structures, Hybrid salts, magnetism, oxalate chromium(III) complex, stoichiometry
Identifiers
Local EPrints ID: 450830
URI: http://eprints.soton.ac.uk/id/eprint/450830
ISSN: 0095-8972
PURE UUID: c4eb6d12-b347-4302-82c6-406d8a7ee10a
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Date deposited: 13 Aug 2021 16:34
Last modified: 18 Mar 2024 02:50
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Contributors
Author:
Coustel M.N. Choubeu
Author:
Bridget N. Ndosiri
Author:
Hervé Vezin
Author:
Claire Minaud
Author:
James B. Orton
Author:
Justin Nenwa
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