TY - JOUR

T1 - Coordination Compound of Copper(II) with an Isonicotinohydrazide Derivative

AU - Fomenko, I. S.

AU - Bakaev, I. V.

AU - Sedykh, E. S.

AU - Abramov, P. A.

AU - Makhmudi, G.

AU - Gushchin, A. L.

N1 - The authors thank the Ministry of Science and Higher Education of the Russian Federation (project No. 121031700315-2) and the XRD Facility of Nikolaev Institute of Inorganic Chemistry. Coordination Compound of Copper(II) with an Isonicotinohydrazide Derivative / I. S. Fomenko, I. V. Bakaev, E. S. Sedykh [et al.] // Journal of Structural Chemistry. – 2024. – Vol. 65, No. 12. – P. 2533-2543. – DOI 10.1134/S0022476624120163.

PY - 2024/12/27

Y1 - 2024/12/27

N2 - Abstract: The {[CuCl(L)]·DMF}n complex compound is prepared by the interaction of (E)-N′-(pyridin-2-ylmethylene)isonicotinohydrazide (L) with CuCl2·2H2O in ethanol. The obtained compound is characterized by elemental analysis and IR spectroscopy; its crystal structure is determined by XRD. The compound has a polymeric structure and is composed of {CuCl(L)} fragments connected into zigzag chains due to the coordination of the pyridine nitrogen of the L ligand of one fragment to the copper atom of the neighboring fragment. The copper ion has a distorted square-pyramidal coordination environment (∠NCuO = 155.71° and ∠NCuCl = 101.16°). The unit cell containing four {[Cu(L)Cl]·DMF} fragments is calculated within the quantum chemical approach of the density functional theory. The electronic structure is analyzed; the band structure and density of states diagrams are constructed. It is shown that the electronic structure has no band gap: the Fermi level virtually coincides with the highest occupied crystal orbital (HOCO) and is equal to –5.733 eV. The HOCO and the lowest unoccupied crystal orbital (LUCO) have similar compositions, but the contribution of p orbitals of the organic ligand is higher for the LUCO. The electron density Laplacian values at the critical points of Cu–N, Cu–Cl, and Cu–O bonds indicate that these bonds belong to the intermediate type with a predominant contribution of ionic bonding.

AB - Abstract: The {[CuCl(L)]·DMF}n complex compound is prepared by the interaction of (E)-N′-(pyridin-2-ylmethylene)isonicotinohydrazide (L) with CuCl2·2H2O in ethanol. The obtained compound is characterized by elemental analysis and IR spectroscopy; its crystal structure is determined by XRD. The compound has a polymeric structure and is composed of {CuCl(L)} fragments connected into zigzag chains due to the coordination of the pyridine nitrogen of the L ligand of one fragment to the copper atom of the neighboring fragment. The copper ion has a distorted square-pyramidal coordination environment (∠NCuO = 155.71° and ∠NCuCl = 101.16°). The unit cell containing four {[Cu(L)Cl]·DMF} fragments is calculated within the quantum chemical approach of the density functional theory. The electronic structure is analyzed; the band structure and density of states diagrams are constructed. It is shown that the electronic structure has no band gap: the Fermi level virtually coincides with the highest occupied crystal orbital (HOCO) and is equal to –5.733 eV. The HOCO and the lowest unoccupied crystal orbital (LUCO) have similar compositions, but the contribution of p orbitals of the organic ligand is higher for the LUCO. The electron density Laplacian values at the critical points of Cu–N, Cu–Cl, and Cu–O bonds indicate that these bonds belong to the intermediate type with a predominant contribution of ionic bonding.

KW - DFT calculations

KW - XRD

KW - coordination polymers

KW - copper

KW - hydrazides

KW - synthesis

UR - https://www.mendeley.com/catalogue/9de54c43-668b-3ef2-914d-fd5e1bfe9ea3/

UR - https://www.scopus.com/record/display.uri?eid=2-s2.0-105000137560&origin=inward&txGid=f56e2bbd2b58fcca621184158be4b321

UR - https://elibrary.ru/item.asp?id=79026296

U2 - 10.1134/S0022476624120163

DO - 10.1134/S0022476624120163

M3 - Article

VL - 65

SP - 2533

EP - 2543

JO - Journal of Structural Chemistry

JF - Journal of Structural Chemistry

SN - 0022-4766

IS - 12

ER -