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Novel dichloro(bis{2-[1-(4-methylphenyl)-1H-1,2,3-triazol-4-yl-κN3]pyridine-κN})metal(II) coordination compounds of seven transition metals (Mn, Fe, Co, Ni, Cu, Zn and Cd)

Novel dichloro(bis{2-[1-(4-methylphenyl)-1H-1,2,3-triazol-4-yl-κN3]pyridine-κN})metal(II) coordination compounds of seven transition metals (Mn, Fe, Co, Ni, Cu, Zn and Cd)
Novel dichloro(bis{2-[1-(4-methylphenyl)-1H-1,2,3-triazol-4-yl-κN3]pyridine-κN})metal(II) coordination compounds of seven transition metals (Mn, Fe, Co, Ni, Cu, Zn and Cd)

The synthesis, characterization, DFT and, in two cases, the structure of seven novel dichloro(bis{2-[1-(4-methylphenyl)-1H-1,2,3-triazol-4-yl-κN3]pyridine-κN})metal(II) coordination compounds ([M(L2)2Cl2]), containing transition metals of groups 7–12, are described. Both experimentally measured magnetic moment and DFT calculations showed that d5 Mn(II) (with µeff = 5.62 B.M., S = 5/2), d6 Fe(II) (with µeff = 5.26 B.M., S = 2), d7 Co(II) (with µeff = 3.98 B.M., S = 3/2), d8 Ni(II) (with µeff = 3.00 B.M., S = 1) and d9 Cu(II) (with µeff = 1.70 B.M., S = ½) are all paramagnetic, while d10 Zn(II) and Cd(II) are diamagnetic with S = 0. DFT calculations on the possible isomers of these coordination compounds, showed that the cis–cis–trans and the trans–trans–trans isomers, with the pyridyl groups trans to each other, are the lowest in energy. The trans–trans–trans isomers were experimentally characterized by X-ray crystallography for [Ni(L2)2Cl2] and [Zn(L2)2Cl2]·L2 in this study. In the solid state the coordination compounds are connected by intermolecular hydrogen bonds, mainly involving the chloride atoms, to form 3D supramolecular structures. Computational chemistry calculations, using Natural Bonding Orbital calculations, identified these inter-molecular hydrogen bonds, C–H⋯Cl, by a donor–acceptor interaction from a filled lone pair NBO on Cl to an empty antibonding NBO on (C–H). The inter-molecular hydrogen bonds were also identified by QTAIM determined bonding paths between Cl and the respective hydrogen. The theoretically calculated computational chemistry results thus give an understanding on a molecular level why in the solid state where inter-molecular forces and packing play a role, the trans–trans–trans isomers are mostly obtained.

(1,2,3-Triazol-4-yl)pyridine, Bonding-path, Coordination compound, DFT, Donor–acceptor
0277-5387
243-254
Conradie, J.
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Conradie, M.M.
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Tawfiq, K.M.
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Al-Jeboori, M.J.
180ff82a-635c-452f-925d-c2034b42765b
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Wilson, C.
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Potgieter, J.H.
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Conradie, J.
814b9b0c-ae44-4f35-b80b-4d27bd575030
Conradie, M.M.
b092ff5b-65d6-4bc6-93f7-2819a613ffaa
Tawfiq, K.M.
1b5acc5d-c8a9-4113-9637-a8b91717912f
Al-Jeboori, M.J.
180ff82a-635c-452f-925d-c2034b42765b
Coles, S.J.
3116f58b-c30c-48cf-bdd5-397d1c1fecf8
Wilson, C.
7a53140a-0079-4aac-8b5a-a375b3659dd2
Potgieter, J.H.
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Conradie, J., Conradie, M.M., Tawfiq, K.M., Al-Jeboori, M.J., Coles, S.J., Wilson, C. and Potgieter, J.H. (2018) Novel dichloro(bis{2-[1-(4-methylphenyl)-1H-1,2,3-triazol-4-yl-κN3]pyridine-κN})metal(II) coordination compounds of seven transition metals (Mn, Fe, Co, Ni, Cu, Zn and Cd). Polyhedron, 151, 243-254. (doi:10.1016/j.poly.2018.03.026).

Record type: Article

Abstract

The synthesis, characterization, DFT and, in two cases, the structure of seven novel dichloro(bis{2-[1-(4-methylphenyl)-1H-1,2,3-triazol-4-yl-κN3]pyridine-κN})metal(II) coordination compounds ([M(L2)2Cl2]), containing transition metals of groups 7–12, are described. Both experimentally measured magnetic moment and DFT calculations showed that d5 Mn(II) (with µeff = 5.62 B.M., S = 5/2), d6 Fe(II) (with µeff = 5.26 B.M., S = 2), d7 Co(II) (with µeff = 3.98 B.M., S = 3/2), d8 Ni(II) (with µeff = 3.00 B.M., S = 1) and d9 Cu(II) (with µeff = 1.70 B.M., S = ½) are all paramagnetic, while d10 Zn(II) and Cd(II) are diamagnetic with S = 0. DFT calculations on the possible isomers of these coordination compounds, showed that the cis–cis–trans and the trans–trans–trans isomers, with the pyridyl groups trans to each other, are the lowest in energy. The trans–trans–trans isomers were experimentally characterized by X-ray crystallography for [Ni(L2)2Cl2] and [Zn(L2)2Cl2]·L2 in this study. In the solid state the coordination compounds are connected by intermolecular hydrogen bonds, mainly involving the chloride atoms, to form 3D supramolecular structures. Computational chemistry calculations, using Natural Bonding Orbital calculations, identified these inter-molecular hydrogen bonds, C–H⋯Cl, by a donor–acceptor interaction from a filled lone pair NBO on Cl to an empty antibonding NBO on (C–H). The inter-molecular hydrogen bonds were also identified by QTAIM determined bonding paths between Cl and the respective hydrogen. The theoretically calculated computational chemistry results thus give an understanding on a molecular level why in the solid state where inter-molecular forces and packing play a role, the trans–trans–trans isomers are mostly obtained.

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Znpyridyl_R1 (1) - Accepted Manuscript
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Accepted/In Press date: 25 March 2018
e-pub ahead of print date: 3 April 2018
Published date: 1 September 2018
Keywords: (1,2,3-Triazol-4-yl)pyridine, Bonding-path, Coordination compound, DFT, Donor–acceptor

Identifiers

Local EPrints ID: 424848
URI: http://eprints.soton.ac.uk/id/eprint/424848
ISSN: 0277-5387
PURE UUID: 1755bf2f-f211-4cb5-b823-ab4378b4615b
ORCID for S.J. Coles: ORCID iD orcid.org/0000-0001-8414-9272

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Date deposited: 05 Oct 2018 11:49
Last modified: 22 Nov 2021 06:46

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Contributors

Author: J. Conradie
Author: M.M. Conradie
Author: K.M. Tawfiq
Author: M.J. Al-Jeboori
Author: S.J. Coles ORCID iD
Author: C. Wilson
Author: J.H. Potgieter

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