Complexes of Ni<sup>II</sup>, Co<sup>II</sup>, Zn<sup>II</sup>, and Cu<sup>II</sup> with Promising Anti-Tuberculosis Drug: Solid-State Structures and DFT Calculations

Four new Ni<sup>II</sup>, Co<sup>II</sup>, Zn<sup>II</sup>, and Cu<sup>II</sup> complexes with the promising anti-tuberculosis drug (<i>E/Z</i>)-N′-((5-Hydroxy-3,4-bis(hydroxymethyl)-6-methylpyridin-2-yl)methylene)-isonicotino-hydrazide (&l...

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Main Authors: Mohamed Ali Ahmed, Maksim A. Zhernakov, Edward M. Gilyazetdinov, Mikhail S. Bukharov, Daut R. Islamov, Konstantin S. Usachev, Alexander E. Klimovitskii, Nikita Yu. Serov, Vladimir A. Burilov, Valery G. Shtyrlin
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Language:English
Published: MDPI AG 2023-04-01
Series:Inorganics
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Online Access:https://www.mdpi.com/2304-6740/11/4/167
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author Mohamed Ali Ahmed
Maksim A. Zhernakov
Edward M. Gilyazetdinov
Mikhail S. Bukharov
Daut R. Islamov
Konstantin S. Usachev
Alexander E. Klimovitskii
Nikita Yu. Serov
Vladimir A. Burilov
Valery G. Shtyrlin
author_facet Mohamed Ali Ahmed
Maksim A. Zhernakov
Edward M. Gilyazetdinov
Mikhail S. Bukharov
Daut R. Islamov
Konstantin S. Usachev
Alexander E. Klimovitskii
Nikita Yu. Serov
Vladimir A. Burilov
Valery G. Shtyrlin
author_sort Mohamed Ali Ahmed
collection DOAJ
description Four new Ni<sup>II</sup>, Co<sup>II</sup>, Zn<sup>II</sup>, and Cu<sup>II</sup> complexes with the promising anti-tuberculosis drug (<i>E/Z</i>)-N′-((5-Hydroxy-3,4-bis(hydroxymethyl)-6-methylpyridin-2-yl)methylene)-isonicotino-hydrazide (<b>L</b>H) were synthesized and characterized by structural methods: single-crystal X-ray diffraction, vibrational spectroscopy, and mass spectrometry. The Ni<sup>II</sup>, Co<sup>II</sup>, and Zn<sup>II</sup> metal ions form only amorphous phases with various morphologies according to mass spectrometry and IR spectroscopy. The Cu<sup>II</sup> forms a crystalline 1D coordination polymer with the relative formula <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mmultiscripts><mrow><mrow><mo>{</mo><mrow><mrow><mo>[</mo><mrow><mi>Cu</mi><mstyle mathvariant="bold" mathsize="normal"><mi>L</mi></mstyle><mi>Cl</mi></mrow><mo>]</mo></mrow><mi>·</mi><mn>0.5</mn><msub><mi mathvariant="normal">H</mi><mn>2</mn></msub><mi mathvariant="normal">O</mi></mrow><mo>}</mo></mrow></mrow><mo>∞</mo><mn>1</mn></mmultiscripts></mrow></semantics></math></inline-formula>. Even though the <b>L</b>H ligand in the crystalline state includes a mixture of <i>E</i>-/<i>Z</i>-isomers, only the tautomeric iminol <i>E</i>-/<i>Z</i>-form is coordinated by Cu<sup>II</sup> in the crystal. The copper(II) complex crystallizes in the monoclinic <i>P</i>2<sub>1</sub>/<i>n</i> space group with the corresponding cell parameters a = 16.3539(11) Å, b = 12.2647(6) Å, and c = 17.4916(10) Å; α = 90°, β = 108.431(7)°, and γ = 90°. DFT calculations showed that the <i>Z</i>-isomer of the <b>L</b>H ligand in solution has the lowest formation energy due to intramolecular hydrogen bonds. According to the quantum chemical calculations, the coordination environment of the Cu<sup>II</sup> atom during the transfer of the molecule into the solution remains the same as in the crystal, except for the polymeric bond, namely, distorted trigonal bipyramidal. Some of the complexes investigated can be used as effective sensors in biosystems.
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spelling doaj.art-8b5641a74b734d45ae9db62e7137f00b2023-11-17T19:45:33ZengMDPI AGInorganics2304-67402023-04-0111416710.3390/inorganics11040167Complexes of Ni<sup>II</sup>, Co<sup>II</sup>, Zn<sup>II</sup>, and Cu<sup>II</sup> with Promising Anti-Tuberculosis Drug: Solid-State Structures and DFT CalculationsMohamed Ali Ahmed0Maksim A. Zhernakov1Edward M. Gilyazetdinov2Mikhail S. Bukharov3Daut R. Islamov4Konstantin S. Usachev5Alexander E. Klimovitskii6Nikita Yu. Serov7Vladimir A. Burilov8Valery G. Shtyrlin9A. M. Butlerov Chemistry Institute, Kazan Federal University, Kremlevskaya St., 18, Kazan 420008, RussiaA. M. Butlerov Chemistry Institute, Kazan Federal University, Kremlevskaya St., 18, Kazan 420008, RussiaA. M. Butlerov Chemistry Institute, Kazan Federal University, Kremlevskaya St., 18, Kazan 420008, RussiaA. M. Butlerov Chemistry Institute, Kazan Federal University, Kremlevskaya St., 18, Kazan 420008, RussiaA. M. Butlerov Chemistry Institute, Kazan Federal University, Kremlevskaya St., 18, Kazan 420008, RussiaLaboratory for Structural Analysis of Biomacromolecules, Kazan Scientific Center of Russian Academy of Science, Kremlevskaya St., 31, Kazan 420008, RussiaA. M. Butlerov Chemistry Institute, Kazan Federal University, Kremlevskaya St., 18, Kazan 420008, RussiaA. M. Butlerov Chemistry Institute, Kazan Federal University, Kremlevskaya St., 18, Kazan 420008, RussiaA. M. Butlerov Chemistry Institute, Kazan Federal University, Kremlevskaya St., 18, Kazan 420008, RussiaA. M. Butlerov Chemistry Institute, Kazan Federal University, Kremlevskaya St., 18, Kazan 420008, RussiaFour new Ni<sup>II</sup>, Co<sup>II</sup>, Zn<sup>II</sup>, and Cu<sup>II</sup> complexes with the promising anti-tuberculosis drug (<i>E/Z</i>)-N′-((5-Hydroxy-3,4-bis(hydroxymethyl)-6-methylpyridin-2-yl)methylene)-isonicotino-hydrazide (<b>L</b>H) were synthesized and characterized by structural methods: single-crystal X-ray diffraction, vibrational spectroscopy, and mass spectrometry. The Ni<sup>II</sup>, Co<sup>II</sup>, and Zn<sup>II</sup> metal ions form only amorphous phases with various morphologies according to mass spectrometry and IR spectroscopy. The Cu<sup>II</sup> forms a crystalline 1D coordination polymer with the relative formula <inline-formula><math xmlns="http://www.w3.org/1998/Math/MathML" display="inline"><semantics><mrow><mmultiscripts><mrow><mrow><mo>{</mo><mrow><mrow><mo>[</mo><mrow><mi>Cu</mi><mstyle mathvariant="bold" mathsize="normal"><mi>L</mi></mstyle><mi>Cl</mi></mrow><mo>]</mo></mrow><mi>·</mi><mn>0.5</mn><msub><mi mathvariant="normal">H</mi><mn>2</mn></msub><mi mathvariant="normal">O</mi></mrow><mo>}</mo></mrow></mrow><mo>∞</mo><mn>1</mn></mmultiscripts></mrow></semantics></math></inline-formula>. Even though the <b>L</b>H ligand in the crystalline state includes a mixture of <i>E</i>-/<i>Z</i>-isomers, only the tautomeric iminol <i>E</i>-/<i>Z</i>-form is coordinated by Cu<sup>II</sup> in the crystal. The copper(II) complex crystallizes in the monoclinic <i>P</i>2<sub>1</sub>/<i>n</i> space group with the corresponding cell parameters a = 16.3539(11) Å, b = 12.2647(6) Å, and c = 17.4916(10) Å; α = 90°, β = 108.431(7)°, and γ = 90°. DFT calculations showed that the <i>Z</i>-isomer of the <b>L</b>H ligand in solution has the lowest formation energy due to intramolecular hydrogen bonds. According to the quantum chemical calculations, the coordination environment of the Cu<sup>II</sup> atom during the transfer of the molecule into the solution remains the same as in the crystal, except for the polymeric bond, namely, distorted trigonal bipyramidal. Some of the complexes investigated can be used as effective sensors in biosystems.https://www.mdpi.com/2304-6740/11/4/167coordination compoundshydrazones<i>d</i>-metalstuberculosisstructuresDFT calculations
spellingShingle Mohamed Ali Ahmed
Maksim A. Zhernakov
Edward M. Gilyazetdinov
Mikhail S. Bukharov
Daut R. Islamov
Konstantin S. Usachev
Alexander E. Klimovitskii
Nikita Yu. Serov
Vladimir A. Burilov
Valery G. Shtyrlin
Complexes of Ni<sup>II</sup>, Co<sup>II</sup>, Zn<sup>II</sup>, and Cu<sup>II</sup> with Promising Anti-Tuberculosis Drug: Solid-State Structures and DFT Calculations
Inorganics
coordination compounds
hydrazones
<i>d</i>-metals
tuberculosis
structures
DFT calculations
title Complexes of Ni<sup>II</sup>, Co<sup>II</sup>, Zn<sup>II</sup>, and Cu<sup>II</sup> with Promising Anti-Tuberculosis Drug: Solid-State Structures and DFT Calculations
title_full Complexes of Ni<sup>II</sup>, Co<sup>II</sup>, Zn<sup>II</sup>, and Cu<sup>II</sup> with Promising Anti-Tuberculosis Drug: Solid-State Structures and DFT Calculations
title_fullStr Complexes of Ni<sup>II</sup>, Co<sup>II</sup>, Zn<sup>II</sup>, and Cu<sup>II</sup> with Promising Anti-Tuberculosis Drug: Solid-State Structures and DFT Calculations
title_full_unstemmed Complexes of Ni<sup>II</sup>, Co<sup>II</sup>, Zn<sup>II</sup>, and Cu<sup>II</sup> with Promising Anti-Tuberculosis Drug: Solid-State Structures and DFT Calculations
title_short Complexes of Ni<sup>II</sup>, Co<sup>II</sup>, Zn<sup>II</sup>, and Cu<sup>II</sup> with Promising Anti-Tuberculosis Drug: Solid-State Structures and DFT Calculations
title_sort complexes of ni sup ii sup co sup ii sup zn sup ii sup and cu sup ii sup with promising anti tuberculosis drug solid state structures and dft calculations
topic coordination compounds
hydrazones
<i>d</i>-metals
tuberculosis
structures
DFT calculations
url https://www.mdpi.com/2304-6740/11/4/167
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