Synthesis, Characterization, and Magnetic Properties of a Series of Copper(II) Chloride Complexes of Pyridyliminebenzoic Acids

E.A. Buvaylo, V.N. Kokozay, V.G Makhankova, A.K. Melnyk, M. Korabik, M. Witwicki, B.W. Skelton, O.Y. Vassilyeva

Research output: Contribution to journalArticle

Abstract

A series of CuII halide complexes, Cu(HL1)Cl2·CH3OH (1), [Cu(L1)Cl]2·H2O (2), [Cu(HL2)Cl2]2·2DMF (3), [Cu(HL2)2Cl]nCln·2nH2O (4), and [Cu(L3)Cl]n (5), containing pyridyliminebenzoic acids HL1, HL2, and HL3 derived from o-, m-, and p-aminobenzoic acids, respectively, have been obtained as single crystals and characterized by elemental analysis, IR, EPR spectroscopy, magnetic measurements, and single-crystal X-ray diffraction techniques. The results obtained show the formation of molecular (1), dimeric (2, 3), and polymeric structures (4, 5) based on chloride (1–4) and carboxylate bridges (5) with copper(II) ions in the square pyramidal geometry of varying degrees of distortion. In the case of 2 and 5 the ligand deprotonation was completely achieved even in the absence of a base. The closest Cu···Cu separations are found in the crystal lattices of the polymer 5 (3.33 Å) and dimers 2 (3.35 Å) and 3 (3.38 Å). The X-band polycrystalline EPR spectra of 1–3 with typical axial patterns show no indication of exchange interactions between copper ions in the range 295–77 K. The observed rhombic features of the EPR spectra of 4 arise from the coupling of g-tensors from differently oriented CuII coordination polyhedra in the solid state. A characteristic spin-triplet EPR spectrum of 5 at 77 K was simulated by using the spin-Hamiltonian parameters for S = 1, gx = 2.08, gy = 2.11, gz = 2.37 and the value of the zero-field splitting parameter D of 0.137 cm–1. Magnetic susceptibility measurements revealed antiferromagnetic (1–3, 5) and ferromagnetic coupling (4) between the metal atoms at low temperatures. Theoretical methods were employed to provide additional insight into magnetic interactions in the studied compounds.

Original languageEnglish
Pages (from-to)1603-1619
Number of pages17
JournalEuropean Journal of Inorganic Chemistry
Volume2018
Issue number14
DOIs
Publication statusPublished - 17 Apr 2018

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Paramagnetic resonance
Magnetic properties
Acids
Copper
Single crystals
Ions
4-Aminobenzoic Acid
Hamiltonians
Deprotonation
Exchange interactions
Magnetic variables measurement
Magnetic susceptibility
Crystal lattices
Dimers
Tensors
Chlorides
Polymers
Metals
Spectroscopy
Ligands

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Buvaylo, E. A., Kokozay, V. N., Makhankova, V. G., Melnyk, A. K., Korabik, M., Witwicki, M., ... Vassilyeva, O. Y. (2018). Synthesis, Characterization, and Magnetic Properties of a Series of Copper(II) Chloride Complexes of Pyridyliminebenzoic Acids. European Journal of Inorganic Chemistry, 2018(14), 1603-1619. https://doi.org/10.1002/ejic.201701391
Buvaylo, E.A. ; Kokozay, V.N. ; Makhankova, V.G ; Melnyk, A.K. ; Korabik, M. ; Witwicki, M. ; Skelton, B.W. ; Vassilyeva, O.Y. / Synthesis, Characterization, and Magnetic Properties of a Series of Copper(II) Chloride Complexes of Pyridyliminebenzoic Acids. In: European Journal of Inorganic Chemistry. 2018 ; Vol. 2018, No. 14. pp. 1603-1619.
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abstract = "A series of CuII halide complexes, Cu(HL1)Cl2·CH3OH (1), [Cu(L1)Cl]2·H2O (2), [Cu(HL2)Cl2]2·2DMF (3), [Cu(HL2)2Cl]nCln·2nH2O (4), and [Cu(L3)Cl]n (5), containing pyridyliminebenzoic acids HL1, HL2, and HL3 derived from o-, m-, and p-aminobenzoic acids, respectively, have been obtained as single crystals and characterized by elemental analysis, IR, EPR spectroscopy, magnetic measurements, and single-crystal X-ray diffraction techniques. The results obtained show the formation of molecular (1), dimeric (2, 3), and polymeric structures (4, 5) based on chloride (1–4) and carboxylate bridges (5) with copper(II) ions in the square pyramidal geometry of varying degrees of distortion. In the case of 2 and 5 the ligand deprotonation was completely achieved even in the absence of a base. The closest Cu···Cu separations are found in the crystal lattices of the polymer 5 (3.33 {\AA}) and dimers 2 (3.35 {\AA}) and 3 (3.38 {\AA}). The X-band polycrystalline EPR spectra of 1–3 with typical axial patterns show no indication of exchange interactions between copper ions in the range 295–77 K. The observed rhombic features of the EPR spectra of 4 arise from the coupling of g-tensors from differently oriented CuII coordination polyhedra in the solid state. A characteristic spin-triplet EPR spectrum of 5 at 77 K was simulated by using the spin-Hamiltonian parameters for S = 1, gx = 2.08, gy = 2.11, gz = 2.37 and the value of the zero-field splitting parameter D of 0.137 cm–1. Magnetic susceptibility measurements revealed antiferromagnetic (1–3, 5) and ferromagnetic coupling (4) between the metal atoms at low temperatures. Theoretical methods were employed to provide additional insight into magnetic interactions in the studied compounds.",
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Synthesis, Characterization, and Magnetic Properties of a Series of Copper(II) Chloride Complexes of Pyridyliminebenzoic Acids. / Buvaylo, E.A.; Kokozay, V.N.; Makhankova, V.G; Melnyk, A.K.; Korabik, M.; Witwicki, M.; Skelton, B.W.; Vassilyeva, O.Y.

In: European Journal of Inorganic Chemistry, Vol. 2018, No. 14, 17.04.2018, p. 1603-1619.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis, Characterization, and Magnetic Properties of a Series of Copper(II) Chloride Complexes of Pyridyliminebenzoic Acids

AU - Buvaylo, E.A.

AU - Kokozay, V.N.

AU - Makhankova, V.G

AU - Melnyk, A.K.

AU - Korabik, M.

AU - Witwicki, M.

AU - Skelton, B.W.

AU - Vassilyeva, O.Y.

PY - 2018/4/17

Y1 - 2018/4/17

N2 - A series of CuII halide complexes, Cu(HL1)Cl2·CH3OH (1), [Cu(L1)Cl]2·H2O (2), [Cu(HL2)Cl2]2·2DMF (3), [Cu(HL2)2Cl]nCln·2nH2O (4), and [Cu(L3)Cl]n (5), containing pyridyliminebenzoic acids HL1, HL2, and HL3 derived from o-, m-, and p-aminobenzoic acids, respectively, have been obtained as single crystals and characterized by elemental analysis, IR, EPR spectroscopy, magnetic measurements, and single-crystal X-ray diffraction techniques. The results obtained show the formation of molecular (1), dimeric (2, 3), and polymeric structures (4, 5) based on chloride (1–4) and carboxylate bridges (5) with copper(II) ions in the square pyramidal geometry of varying degrees of distortion. In the case of 2 and 5 the ligand deprotonation was completely achieved even in the absence of a base. The closest Cu···Cu separations are found in the crystal lattices of the polymer 5 (3.33 Å) and dimers 2 (3.35 Å) and 3 (3.38 Å). The X-band polycrystalline EPR spectra of 1–3 with typical axial patterns show no indication of exchange interactions between copper ions in the range 295–77 K. The observed rhombic features of the EPR spectra of 4 arise from the coupling of g-tensors from differently oriented CuII coordination polyhedra in the solid state. A characteristic spin-triplet EPR spectrum of 5 at 77 K was simulated by using the spin-Hamiltonian parameters for S = 1, gx = 2.08, gy = 2.11, gz = 2.37 and the value of the zero-field splitting parameter D of 0.137 cm–1. Magnetic susceptibility measurements revealed antiferromagnetic (1–3, 5) and ferromagnetic coupling (4) between the metal atoms at low temperatures. Theoretical methods were employed to provide additional insight into magnetic interactions in the studied compounds.

AB - A series of CuII halide complexes, Cu(HL1)Cl2·CH3OH (1), [Cu(L1)Cl]2·H2O (2), [Cu(HL2)Cl2]2·2DMF (3), [Cu(HL2)2Cl]nCln·2nH2O (4), and [Cu(L3)Cl]n (5), containing pyridyliminebenzoic acids HL1, HL2, and HL3 derived from o-, m-, and p-aminobenzoic acids, respectively, have been obtained as single crystals and characterized by elemental analysis, IR, EPR spectroscopy, magnetic measurements, and single-crystal X-ray diffraction techniques. The results obtained show the formation of molecular (1), dimeric (2, 3), and polymeric structures (4, 5) based on chloride (1–4) and carboxylate bridges (5) with copper(II) ions in the square pyramidal geometry of varying degrees of distortion. In the case of 2 and 5 the ligand deprotonation was completely achieved even in the absence of a base. The closest Cu···Cu separations are found in the crystal lattices of the polymer 5 (3.33 Å) and dimers 2 (3.35 Å) and 3 (3.38 Å). The X-band polycrystalline EPR spectra of 1–3 with typical axial patterns show no indication of exchange interactions between copper ions in the range 295–77 K. The observed rhombic features of the EPR spectra of 4 arise from the coupling of g-tensors from differently oriented CuII coordination polyhedra in the solid state. A characteristic spin-triplet EPR spectrum of 5 at 77 K was simulated by using the spin-Hamiltonian parameters for S = 1, gx = 2.08, gy = 2.11, gz = 2.37 and the value of the zero-field splitting parameter D of 0.137 cm–1. Magnetic susceptibility measurements revealed antiferromagnetic (1–3, 5) and ferromagnetic coupling (4) between the metal atoms at low temperatures. Theoretical methods were employed to provide additional insight into magnetic interactions in the studied compounds.

KW - Aminobenzoic acids

KW - Copper

KW - Density functional calculations

KW - Magnetic properties

KW - N,O ligands

KW - Schiff bases

KW - Structure elucidation

KW - X-ray diffraction

UR - http://www.scopus.com/inward/record.url?scp=85045682804&partnerID=8YFLogxK

U2 - 10.1002/ejic.201701391

DO - 10.1002/ejic.201701391

M3 - Article

VL - 2018

SP - 1603

EP - 1619

JO - European Journal of Inorganic Chemistry

JF - European Journal of Inorganic Chemistry

SN - 1099-0682

IS - 14

ER -