Synthesis, crystallization and Hirshfeld surface analysis of transition metal carboxylate pentapyridines

Marissa K. Melvin; Brian W. Skelton; Paul K. Eggers; Colin L. Raston

doi:10.1039/d1ce01248g

Synthesis, crystallization and Hirshfeld surface analysis of transition metal carboxylate pentapyridines

Marissa K. Melvin, Brian W. Skelton, Paul K. Eggers, Colin L. Raston

School of Molecular Sciences

Research output: Contribution to journal › Article › peer-review

12 Citations (Scopus)

Abstract

A new compound 2,6-bis(1,1-di(pyridin-2-yl)ethyl)isonicotinic acid (Py5Me₂COOH) was successfully synthesised and metalated with nickel, cobalt and copper to give the corresponding complexes [Co(Py5Me₂COO⁻)(OH⁻)]¹⁺(1), [Ni(Py5Me₂COO⁻)(H₂O)]¹⁺(2) and [Cu₄(Py5Me₂COO⁻)₂(H₂O)₄(OH⁻)₂]⁴⁺(3). The complexes were characterized through HD-MS, FT-IR and UV-vis spectroscopic methods. Crystals suitable for single X-ray diffraction were successfully grown and reveals complex1and2maintain the conventional distorted octahedral configuration. Complex3resulted in the formation of a square pyramidal tetra-copper di-ligand structure. Hirshfeld surfaces mapped withd_normand shape index functions were used to give further information on interaction types within the crystal. Analysis of the 2D fingerprint plots shows the dominant interactions within the crystal packing to be H⋯H and O⋯H contacts, with complex1forming a three-dimensional hydrogen bonded polymer. Crystal packing in complex3is strongly influenced by fluorine interactions; (H⋯F) and the packing structure of complex2is shaped by π based interactions. The orientation of these contacts reveals the structure directing effects of the carboxylate, with the weaker aromatic interactions arranging to give priority to the stronger and more directional hydrogen bonds.

Original language	English
Pages (from-to)	57-69
Number of pages	13
Journal	CrystEngComm
Volume	24
Issue number	1
DOIs	https://doi.org/10.1039/d1ce01248g
Publication status	Published - 7 Jan 2022

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title = "Synthesis, crystallization and Hirshfeld surface analysis of transition metal carboxylate pentapyridines",

abstract = "A new compound 2,6-bis(1,1-di(pyridin-2-yl)ethyl)isonicotinic acid (Py5Me2COOH) was successfully synthesised and metalated with nickel, cobalt and copper to give the corresponding complexes [Co(Py5Me2COO−)(OH−)]1+(1), [Ni(Py5Me2COO−)(H2O)]1+(2) and [Cu4(Py5Me2COO−)2(H2O)4(OH−)2]4+(3). The complexes were characterized through HD-MS, FT-IR and UV-vis spectroscopic methods. Crystals suitable for single X-ray diffraction were successfully grown and reveals complex1and2maintain the conventional distorted octahedral configuration. Complex3resulted in the formation of a square pyramidal tetra-copper di-ligand structure. Hirshfeld surfaces mapped withdnormand shape index functions were used to give further information on interaction types within the crystal. Analysis of the 2D fingerprint plots shows the dominant interactions within the crystal packing to be H⋯H and O⋯H contacts, with complex1forming a three-dimensional hydrogen bonded polymer. Crystal packing in complex3is strongly influenced by fluorine interactions; (H⋯F) and the packing structure of complex2is shaped by π based interactions. The orientation of these contacts reveals the structure directing effects of the carboxylate, with the weaker aromatic interactions arranging to give priority to the stronger and more directional hydrogen bonds.",

author = "Melvin, {Marissa K.} and Skelton, {Brian W.} and Eggers, {Paul K.} and Raston, {Colin L.}",

year = "2022",

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AU - Skelton, Brian W.

AU - Eggers, Paul K.

AU - Raston, Colin L.

PY - 2022/1/7

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N2 - A new compound 2,6-bis(1,1-di(pyridin-2-yl)ethyl)isonicotinic acid (Py5Me2COOH) was successfully synthesised and metalated with nickel, cobalt and copper to give the corresponding complexes [Co(Py5Me2COO−)(OH−)]1+(1), [Ni(Py5Me2COO−)(H2O)]1+(2) and [Cu4(Py5Me2COO−)2(H2O)4(OH−)2]4+(3). The complexes were characterized through HD-MS, FT-IR and UV-vis spectroscopic methods. Crystals suitable for single X-ray diffraction were successfully grown and reveals complex1and2maintain the conventional distorted octahedral configuration. Complex3resulted in the formation of a square pyramidal tetra-copper di-ligand structure. Hirshfeld surfaces mapped withdnormand shape index functions were used to give further information on interaction types within the crystal. Analysis of the 2D fingerprint plots shows the dominant interactions within the crystal packing to be H⋯H and O⋯H contacts, with complex1forming a three-dimensional hydrogen bonded polymer. Crystal packing in complex3is strongly influenced by fluorine interactions; (H⋯F) and the packing structure of complex2is shaped by π based interactions. The orientation of these contacts reveals the structure directing effects of the carboxylate, with the weaker aromatic interactions arranging to give priority to the stronger and more directional hydrogen bonds.

AB - A new compound 2,6-bis(1,1-di(pyridin-2-yl)ethyl)isonicotinic acid (Py5Me2COOH) was successfully synthesised and metalated with nickel, cobalt and copper to give the corresponding complexes [Co(Py5Me2COO−)(OH−)]1+(1), [Ni(Py5Me2COO−)(H2O)]1+(2) and [Cu4(Py5Me2COO−)2(H2O)4(OH−)2]4+(3). The complexes were characterized through HD-MS, FT-IR and UV-vis spectroscopic methods. Crystals suitable for single X-ray diffraction were successfully grown and reveals complex1and2maintain the conventional distorted octahedral configuration. Complex3resulted in the formation of a square pyramidal tetra-copper di-ligand structure. Hirshfeld surfaces mapped withdnormand shape index functions were used to give further information on interaction types within the crystal. Analysis of the 2D fingerprint plots shows the dominant interactions within the crystal packing to be H⋯H and O⋯H contacts, with complex1forming a three-dimensional hydrogen bonded polymer. Crystal packing in complex3is strongly influenced by fluorine interactions; (H⋯F) and the packing structure of complex2is shaped by π based interactions. The orientation of these contacts reveals the structure directing effects of the carboxylate, with the weaker aromatic interactions arranging to give priority to the stronger and more directional hydrogen bonds.

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Synthesis, crystallization and Hirshfeld surface analysis of transition metal carboxylate pentapyridines

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