Koshenskova, Kseniya A

Koshenskova K.A., Makarenko N.V., Dolgushin F.M., Yambulatov D.S., Bekker O.B., Fedin M.V., Dementev S.A., Krumkacheva O.A., Eremenko I.L., Lutsenko I.A.

The interaction of sodium phytate hydrate C6H18O24P6·xNa·yH2O (phytNa) with Cu(OAc)2·H2O and 1,10-phenanthroline (phen) led to the anionic tetranuclear complex [Cu4(H2O)4(phen)4(phyt)]·2Na+·2NH4+·32H2O (1), the structure of the latter was determined by X-ray diffraction analysis. The phytate 1 is completely deprotonated; six phosphate− fragments (with atoms P1–P6) are characterized by different spatial arrangements relative to the cyclohexane ring (1a5e conformation), which determines two different types of coordination to the complexing agents—P1 and P3, P4, and P6 have monodentate, while P2 and P5 are bidentately bound to Cu2+ cations. The molecular structure of the anion complex is stabilized by a set of strong intramolecular hydrogen bonds involving coordinated water molecules. Aromatic systems of phen ligands chelating copper ions participate in strong intramolecular and intermolecular π-π interactions, further contributing to their association. At the supramolecular level, endless stacks are formed, in the voids of which sodium and ammonium cations and water molecules are present. The stability of 1 in the presence of human serum albumin (HSA) was investigated using Electron Paramagnetic Resonance (EPR) spectroscopy. Continuous wave (CW) EPR spectra in water/glycerol frozen solution clearly indicate a presence of an exchange-coupled Cu(II)-Cu(II) dimeric unit, as well as a Cu(II) monomer-like signal arising from spins sufficiently distant from each other, with comparable contributions of two types of signals. In the presence of albumin at a 1:1 ratio (1 to albumin), the EPR spectrum changes significantly, primarily due to the reduced contribution of the S = 1 fraction showing dipole–dipole splitting. The biological activity of 1 in vitro against the non-pathogenic (model for Mycobacterium tuberculosis) strain of Mycolicibacterium smegmatis is comparable to the first-line drug for tuberculosis treatment, rifampicin.

Koshenskova K.A., Baravikov D.E., Razvorotneva L.S., Dolgushin F.M., Bekker O.B., Khoroshilov A.V., Eremenko I.L., Lutsenko I.A.

The reactions of copper(ii) and zinc(ii) acetates with anions of 5-phenylfuran-2-carboxylic acid (Hphfur) and 5-nitro-1,10-phenanthroline (nphen) or 2,2′-bipyridine (2,2′-bpy) in the MeOH/MeCN system afforded mononuclear complexes of the composition [Cu(phfur)2(nphen)H2O] (1) and [Zn(phfur)2(2,2′-bpy)]•H2O (2). The structures of these complexes were determined by X-ray diffraction analysis (XRD). According to the XRD data, the copper atom in molecular complex 1 is in a distorted square-pyramidal environment (SQ(CuN2O3) = 0.68); the zinc atom in molecular complex 2, in a distorted trigonal-bipyramidal environment (SQ(ZnN2O3) = 3.87). The supramolecular level of 1 is mediated by intermolecular π–π interactions between the aromatic moieties of the ligands and represents a 3D supramolecular structure. in the structure of 2, the water molecules of crystallization are involved in intermolecular hydrogen bonds, resulting in the formation of centrosymmetric hydrogen-bonded dimers. The supramolecular level of 2 is mediated by C—H⋯O and C—H⋯π interactions. According to the simultaneous thermal analysis, complexes 1 and 2 are characterized by different types of thermal destruction. Thus, the explosophoric groups in the ligands of compound 1 are responsible for an intense exothermic effect. The results of biological assays show a certain correlation between the type of the substituted moiety in the heterocycle and the activity against the non-pathogenic Mycolicibacterium smegmatis strain.

Koshenskova K.A., Baravikov D.E., Kayukova L.A., Ergalieva E.M., Nelyubina Y.V., Nikiforova M.E., Dolgushin F.M., Fedin M.V., Bekker O.B., Shender V.O., Malyants I.K., Aliev T.M., Titov K.O., Eremenko I.L., Lutsenko I.A.

Two cationic and molecular copper(II) complexes - mixed ligand [{Cu(phen)2benz}{Cu(phen)2Cl}]2+·2Cl-·benz-·H3O+·4·.5H2O (1), [Cu(benz)2phen] (2) (benz- = m-Cl-benzoate anion; phen = 1,10-phenantroline) and [Cu(phen)3]2+·2OTf-·2EtOH (3) (OTf = trifluoromethylsulfonate, triflate anion, CF3SO3-) were synthesized using various synthetic approaches and thoroughly characterized by spectroscopic methods and single crystal X-ray diffraction analysis. The structures of the complexes according to X-ray diffraction data are characterized by a diverse geometric environment of the complexing agent - the cationic form of 1 comprises two structurally nonequivalent moieties: the Cu (1) and Cu (2) complex-forming atoms coordinate, in chelate manner, two phen moieties each and the benz- (1)/Cl- (2) anions, respectively, thus forming different-ligand formula units, a trigonal–bipyramidal {Cu(1)N4Cl} and a pseudo octahedral one {Cu(2)N4O2}. The copper(II) ion in the complex 2 coordinates one phen ligand in a bidentate mode and two benz- anions to produce a distorted planar square environment {CuN2O2}. In complex 3, the copper(II) cation is surrounded by three phenanthroline fragments {Cu(phen)3}2+ and non-coordinated OTf- ions. The results of an EPR study 1 show that in the solid phase, intermolecular exchange interactions that cause exchange narrowing of the spectrum are efficient, whereas in solutions, resolved spectra of copper(II) ion with rhombic symmetry of the g-tensor are observed. An in vitro study of the biological properties of 1–3 toward nonpathogenic mycobacterial strain Mycolicibacterium smegmatis showed an increase in biological effectiveness depending on the structure of complexes (MIC, 1 (2 nmol/disk) > 3 (5 nmol/disk) > 2 (12.5 nmol/disk)). Complex 1 was also tested for antitumor activity against an ovarian adenocarcinoma SKOV3 demonstrated high efficiency: the IC50 value is almost 9 times higher than the activity of cisplatin.

Koshenskova K.A., Nebykov D.N., Razvalyaeva A.V., Panov A.O., Mokhov V.M., Dolgushin F.M., Baravikov D.E., Simonenko N.P., Simonenko T.L., Shtyrlin V.G., Ermolaev A.V., Fedin M.V., Khoroshilov A.V., Eremenko I.L., Lutsenko I.A.

The reaction of copper(II) acetate with furoic acids (2Hfur / 3Hfur) and imidazole (Im) in methanol resulted in mononuclear complexes [Cu(fur)2(Im)2(H2O)]·L (fur- = 2fur- (1, 2), 3fur- (3); L = MeCN (1)) whose structures were determined by direct single crystal X-ray analysis. It was found for the first time that copper nanoparticles immobilized on the surface of γ-Al2O3 obtained by chemical reduction of 1, 2 and 3 (pre-deposited on the surface from solution) with sodium tetrahydroborate show high selectivity of mono- and dihydrogenation of tricyclo[5.2.1.02,6]deca-3,8-diene (dicyclopentadiene, DCPD). The catalytic activity tests show a high selectivity (97 %) of the catalyst obtained from an ethanolic solution of complex 1 in the reaction of partial hydrogenation to DHDCPD under continuous process conditions even at high conversion values (up to 96 %) and with an excess of hydrogen, whereas the catalyst obtained from an aqueous solution of complex 1 showed 98 % total hydrogenation product (THDCPD) selectivity. The catalysts based on all the complexes 1–3 were successfully used in reactions of nitrobenzene (NB) reduction to aniline (AN) and in the reductive alkylation of nitrobenzene with isobutanol (i-BAN) 100 % yields of aniline and N-isobutylaniline were obtained at LHSV 0.16 h−1.

Koshenskova K.A., Makarenko N.V., Baravikov D.E., Dolgushin F.M., Bekker O.B., Eremenko I.L., Lutsenko I.A.

The reactions in the Cu(OAc)2⋅H2O–phytic acid–2,2'-bipyridine (bpy) system in aqueous methanol solutions resulted in the formation of a molecular different-ligand tetranuclear complex [(Cu4(bpy)4(PO4)2(CO3)(H2O)2]⋅13H2O (I), the structure of which was established from the X-ray diffraction data (CCDC no. 2262998). The molecule of complex I contains four non-equivalent Cu2+ cations, coordinating each two phosphate anions ( $${\text{PO}}_{4}^{{3 - }}$$ remaining after the transformation of the phytate ring), four neutral bpy molecules, two water molecules, and one carbonate anion ( $${\text{CO}}_{3}^{{2 - }}$$ ). The presence of a large number of solvate water molecules in the outer coordination sphere gives rise to a hydrogen-bonded framework involved in stabilization of the crystal packing. Study of the antimycobacterial activity of I against non-pathogenic Mycolicibacterium smegmatis strain revealed high biological efficacy.

Koshenskova K.A., Baravikov D.E., Nelyubina Y.V., Primakov P.V., Shender V.O., Maljants I.K., Bekker O.B., Aliev T.M., Borodin E.A., Kotel’nikov D.D., Leusova N.Y., Mantrov S.N., Kiskin M.A., Eremenko I.L., Lutsenko I.A.

The reaction of copper(II) acetate with 2-furancarboxylic (HFur)/5-nitro-2-furancarboxylic (HNfur) acids and 5-nitro-1,10-phenanthroline (Nphen) in methanol resulted in the formation of the binuclear coordination compounds [Cu2(L)4(Nphen)2]·X (L = Fur (I), Nfur (II); X = H2O (I)), which were structurally studied by direct X-ray diffraction (CCDC no. 2244205 (I) and 2244206 (II)). According to X-ray diffraction data, the coordination environment of the central metal ion in I and II is composed of two nitrogen atoms of Nphen and three oxygen atoms of the acid anions, which thus form the {CuN2O3} tetragonal pyramid in which the copper coordination number is five. Intermolecular hydrogen bonds and stacking interactions between the Nphen aromatic rings provide supramolecular stabilization of I and II. A characteristic feature of supramolecular organization of II is the presence of a coordination bond between the Cu2+ cation and oxygen of the Nphen $${\text{NO}}_{2}^{ - }$$ group of parallel chains. A biological activity assay for complexes I and II concerning the cytotoxic properties against a human ovarian adenocarcinoma cell line (SKOV3) and the mycobacterial strain Mycolicibacterium smegmatis showed an efficient suppression of cell viability. The results of mathematical modeling of the probability of Cu2+ binding to amino acid residues of M. smegmatis proteins suggested the affinity of the Cu(II) ion to a number of amino acids in polypeptide sites. It was shown that metal ion binding in mycobacterial proteins is more characteristic of histidine- and glutamic acid-containing moieties.

Koshenskova K.A., Baravikov D.E., Khoroshilov A.V., Nelyubina Y.V., Primakov P.V., Bekker O.B., Dokuchaeva K.S., Dolgushin F.M., Kiskin M.A., Eremenko I.L., Lutsenko I.A.

Polymer complexes of the composition {[Cu2(fur)4(bpy)]n • nMeOH} (1) and {[Ag3(fur)(bpy)4]n•2nfur·13.5nH2O} (2) were synthesized by the reactions of copper(ii) and silver(i) acetates, respectively, with anions of furancarboxylic acid (Hfur) and 4,4’-bi-pyridine (bpy) under different synthesis conditions. The structures of the new complexes were established by X-ray diffraction (XRD) analysis. According to the XRD data, complex 1 is a polymer, in which the molecular metal oxide moieties are connected in a monodentate manner through bpy to form a 1D structural motif. The coordination environment of the copper(ii) atom in complex 1 can be described as a square pyramid {CuO4N}; the coordination number is 5. ionic complex 2 contains three nonequivalent Agi atoms in different coordination environment with different coordination numbers of the complexing metal (CNAg(1) = 4; CNAg(2)Ag(3) = 2). The supramolecular level of complex 2 is a 3D structure stabilized by different types of interactions, such as hydrogen bonds, π-stacking and ar-gentophilic interactions. The simultaneous thermal analysis demonstrated that complex 1 undergoes desolvation and decarboxylation at temperatures below 234 °C, whereas the bipyridine moieties coordinated to the copper(ii) atoms are not completely eliminated even at 500 °C. The in vitro biological activity of complexes 1 and 2 was evaluated against the non-pathogenic mycobacterial strain Mycolicibacterium smegmatis.

Koshenskova K.A., Lutsenko I.A., Nebykov D.N., Mokhov V.M., Nelyubina Y.V., Primakov P.V., Popov Y.V., Khoroshilov A.V., Kottsov S.Y., Kiskin M.A., Eremenko I.L.

Two new copper complexes with anions derived from 3-furancarboxylic/ 5-nitro-2-furancarboxylic acid and 4-phenylpyridine were obtained. These catalysts are the first example of copper catalysts for the selective hydrogenation of dicyclopentadiene in flow type reactors. The reaction of copper(II) acetate with 3-furancarboxylic acid (Hfur) and 5-nitro-2-furancarboxylic acid (Hnfur) with participation of 4-phenylpyridine (phpy) in acetonitrile resulted in mononuclear complexes [Cu(L) 2 (phpy) 2 (H 2 O)]·solv (L = fur ( 1 ), nfur ( 2 ); solv = phpy ( 1 )) whose structures were determined by direct single crystal X-ray analysis. According to X-ray data, the complexing component in 1 and 2 is in a distorted square-pyramidal environment (CuN 2 O 3 ); the pyramid base is formed by monodentate-bound oxygen atoms of fur - /nfur - anions and a pair of nitrogen atoms of the phpy moieties, while the water molecule occupies an axial position. It was found for the first time that copper nanoparticles immobilized on the surface of γ-Al 2 O 3 obtained by chemical reduction of 1 and 2 (pre-deposited on the surface from solution) with sodium tetrahydroborate show high selectivity of monohydrogenation of tricyclo[5.2.1.0 2,6 ]deca-3,8-diene (dicyclopentadiene, DCPD) to give tricyclo[5.2.1.0 2,6 ]dec-4-ene (5,6-dihydrocyclopentadiene, DHDCPD). The catalytic activity tests show high selectivity (up to 100%) of the catalysts studied in the reaction of partial hydrogenation to DHDCPD under continuous process conditions even at high conversion values (up to 96%) and with hydrogen present in excess. Thermal behavior of 1 and 2 was studied by simultaneous thermal analysis (STA).

Lutsenko I.A., Vologzhanina A.V., Kayukova L.A., Yergalieva E.M., Koshenskova K.A., Bekker O.B., Dorovatovskii P.V., Eremenko I.L.

Koshenskova K.A., Lutsenko I.A., Nelyubina Y.V., Primakov P.V., Aliev T.M., Bekker O.B., Khoroshilov A.V., Mantrov S.N., Kiskin M.A., Eremenko I.L.

Reaction of copper(II) acetate with 5-nitro-2-furoic acid (NO2-Hfur) and N-donor ligands 2,2'‑bipyridine (bpy) and pyridine (py) has resulted in complexes [Cu(NO2-fur)2(H2O)2]·2H2O (I), [Cu(NO2-fur)2(py)2(H2O)] (II), and binuclear [Cu2(NO2-fur)4(bpy)2]·H2O (III) whose structure was determined by X‑ray diffraction study. Cation Cu2+ is in square-planar (I) or square-pyramidal (II, III) environment and has CN(Cu) = 4 (I) or 5 (II, III), respectively. Stability of complexes I–III in solid phase has been determined by synchronous thermal analysis, stability in solutions has been studied by electronic absorption spectroscopy. Compounds I and II are thermally stable (>100°С). The presence of nitro group in the complexes causes strong exothermal effects, whose intensity is leveled by donor ligand. The storage of solutions of the compounds in 5% glucose solution and 0.9% NaCl for 2 days according to UV spectroscopy causes no their degradation. Biological activity of complexes I–III was studied in vitro toward non-pathogenic strain M. smegmatis (behaves as a model for M. tuberculosis); antimicrobial activity of compound II toward a number of Gram-positive and Gram-negative bacteria has been investigated.

Lutsenko I.A., Baravikov D.E., Koshenskova K.A., Kiskin M.A., Nelyubina Y.V., Primakov P.V., Voronina Y.K., Garaeva V.V., Aleshin D.A., Aliev T.M., Danilenko V.N., Bekker O.B., Eremenko I.L.

New complexes of zinc(ii) and copper(ii) with 2-furoic acid (Hfur), acetic acids and N-donor ligands with the compositions [Zn2(fur)4]n, [Zn2(fur)4(NH2py)2], [Zn(fur)2(neoc)], [Zn(OAc)2(neoc)], and [Cu(fur)2(neoc)(H2O)] were synthesized.

Луценко И.А., Никифорова М.Е., Кошенскова К.А., Кискин М.А., Нелюбина Ю.В., Примаков П.В., Федин М.В., Беккер О.Б., Шендер В.О., Мальянц И.К., Еременко И.Л.

Lutsenko I.A., Nikiforova M.E., Koshenskova K.A., Kiskin M.A., Nelyubina Y.V., Primakov P.V., Fedin M.V., Becker O.B., Shender V.O., Malyants I.K., Eremenko I.L.

Using the reactions of copper(II) acetate magnesium(II) oxide with 2-furancarboxylic acid (HFur), compounds with chemical compositions [Cu2(Fur)4(MeCN)2] (I) and [Mg2(Fur)4(H2O)5]∙ MeCN∙H2O (II) are synthesized. According to the X-ray diffraction data (CIF files CCDC nos. 2085817 (I) and 2085818 (II)), both complexes have a binuclear structure. The metal core of I correspond to the tetracarboxylate bridged {Cu2(μ-Fur)4} complex, the coordination number of the copper atom in which is 5 (CuNO4); in II, the metal atoms are linked by two carboxylate groups and a water molecule, and the coordination environment of the metal centers is completed to the polyhedron (MgO6) by oxygen atoms of the Fur– anions and water molecules. According to EPR spectroscopy data, exchange-coupled copper(II) dimers with a substantial zero-field splitting are observed in I. For I and II, antibacterial activity against the nonpathogenic strain of M. smegmatis, and cytotoxicity against human ovarian adenocarcinoma cells SCOV3 and normal human fibroblast cells of the HDF line have been determined.

Lutsenko I.A., Kiskin M.A., Koshenskova K.A., Primakov P.V., Khoroshilov A.V., Bekker O.B., Eremenko I.L.

The reaction of copper(ii) acetate with 2-furancarboxylate (Hfur, pyromucate) anions and the N-donor ligands 4-phenylpyridine (phpy) and 3-aminopyridine (NH2py) in acetonitrile afforded the mononuclear complexes of the composition [Cu(fur)2(phpy)2(H2O)] · phpy (1) and [Cu(fur)2(NH2py)2] (2), respectively. The structures of the complexes were established by X-ray diffraction. The simultaneous thermal analysis of the thermal behavior of complex 1 showed that this complex is thermally stable up to 125 °C. The in vitro biological activity of complexes 1 and 2 was evaluated against the non-pathogenic mycobacterial Mycolicibacterium smegmatis strain.

Amin M., Diker H., Şahin O., Varlikli C., Soliman A.

ABSTRACTTwo copper and cobalt complexes based on 3‐(trifluoromethyl)‐4‐((3‐(trifluoromethyl)phenyl)diazenyl)‐1H‐pyrazol‐5‐ol (Httdp) have been prepared and characterized using different physicochemical techniques. The crystal structure of the copper complex has been proven to be a square pyramidal, and the cobalt complex has an octahedral structure. DFT calculations of the complexes were performed, and the energy gaps between the HOMO–LUMO of the complexes (−3.38676 to −3.18138 eV) and the Cu (II) complex reflect a higher relative stability compared with Httdp and the Co (II) complex. The antibacterial activities of the two complexes were evaluated. The Co (II) complex demonstrated the highest antibacterial activity against various bacteria compared with Httdp and the Cu (II) complex. The mean inhibition zones exhibited by the Co (II) complex showed the highest activities toward the Gram‐negative bacterial strains with mean inhibition zones of 30.3 ± 0.6 (Staphylococcus aureus) and 25.7 ± 0.6 (Bacillus subtilis) mm. Docking studies were carried out using S. aureus tyrosyl‐tRNA synthetase (PDB ID: 1JIJ) to assess the antimicrobial activities, proving that the complexes were efficient for the protein.

Uvarova M.A., Dolgushin F.M., Metlin M.T., Metlina D., Taydakov I.V., Shender V.O., Bekker O., Lutsenko I., Eremenko I.

Heteroleptic Zn2Gd2 and Zn2Eu2 complexes have been synthesized and their photophisical properties have been investigated. The complexes demonstrate antibacterial activity and cytotoxic effect on the cancer cells higher than on healthy fibroblasts.

Koshenskova K.A., Makarenko N.V., Dolgushin F.M., Yambulatov D.S., Bekker O.B., Fedin M.V., Dementev S.A., Krumkacheva O.A., Eremenko I.L., Lutsenko I.A.

The interaction of sodium phytate hydrate C6H18O24P6·xNa·yH2O (phytNa) with Cu(OAc)2·H2O and 1,10-phenanthroline (phen) led to the anionic tetranuclear complex [Cu4(H2O)4(phen)4(phyt)]·2Na+·2NH4+·32H2O (1), the structure of the latter was determined by X-ray diffraction analysis. The phytate 1 is completely deprotonated; six phosphate− fragments (with atoms P1–P6) are characterized by different spatial arrangements relative to the cyclohexane ring (1a5e conformation), which determines two different types of coordination to the complexing agents—P1 and P3, P4, and P6 have monodentate, while P2 and P5 are bidentately bound to Cu2+ cations. The molecular structure of the anion complex is stabilized by a set of strong intramolecular hydrogen bonds involving coordinated water molecules. Aromatic systems of phen ligands chelating copper ions participate in strong intramolecular and intermolecular π-π interactions, further contributing to their association. At the supramolecular level, endless stacks are formed, in the voids of which sodium and ammonium cations and water molecules are present. The stability of 1 in the presence of human serum albumin (HSA) was investigated using Electron Paramagnetic Resonance (EPR) spectroscopy. Continuous wave (CW) EPR spectra in water/glycerol frozen solution clearly indicate a presence of an exchange-coupled Cu(II)-Cu(II) dimeric unit, as well as a Cu(II) monomer-like signal arising from spins sufficiently distant from each other, with comparable contributions of two types of signals. In the presence of albumin at a 1:1 ratio (1 to albumin), the EPR spectrum changes significantly, primarily due to the reduced contribution of the S = 1 fraction showing dipole–dipole splitting. The biological activity of 1 in vitro against the non-pathogenic (model for Mycobacterium tuberculosis) strain of Mycolicibacterium smegmatis is comparable to the first-line drug for tuberculosis treatment, rifampicin.

Uvarova M.A., Dolgushin F.M., Babeshkin K.A., Efimov N.N., Gogoleva N.V., Nebykov D.N., Lagutina A.V., Panov A.O., Mokhov V.M., Bekker O.B., Titov K.O., Lutsenko I.A., Eremenko I.L.

Charitha K.R., Rani R.M., Kavitha P.

A ligand has been synthesized from 1-(1-methyl-5-(tosylamino)-1H-1,2,3-triazol-4-yl)ethanone and dimethylpyrimidyl hydrazone, and its copper(II), nickel(II), and zinc(II) complexes have been produced and analyzed. The X-ray diffraction analysis shows that the zinc(II) combination with the N3O donor ligand environment has the form of a tetragonal pyramid. The chelate core of the copper(II) complex is structurally identical, as shown by X-ray data. The coordination core of the nickel(II) complex is an octahedron, which is completed by the solvent molecule. Pharmacological evidence of antibacterial activity was obtained for all the substances. The synthetic compounds have been studied and compared to existing antibiotics like chloramphenicol and amphotericin B for their ability to kill bacteria and fungi, respectively.

Uvarova M.A., Shmelev M.A., Nefedov S.E.

The reaction of the mononuclear complex [PhenCu(OOCtBu)2(H2O)] (I) with [PhenCu(CH3CN)(Otf)2] (Phen = 1,10-phenanthroline, Otf = CF3S $${\text{O}}_{3}^{ - }$$ ) in dichloromethane at room temperature gave the binuclear complex [Phen2Cu2(µ-OOCtBu)2(Otf)2] (II). The reaction of II with pyrazole (PzH) involved the displacement of the triflate anions to the outer sphere and gave the ionic complex [Phen2Cu2(µ-OOCtBu)2(PzH)2](Otf)2 (III), while a similar reaction with 3,5-bis(trifluoromethyl)pyrazole ((CF3)2PzH) was accompanied by its deprotonation and gave the heteroleptic complex [Phen2Cu2(µ-OOCtBu)(µ-(CF3)2Pz)(µ-Otf)]Otf (IV). Compounds I–IV were characterized by X-ray diffraction (CCDC nos. 2332399 (I), 2332400 (II), 2332402 (III), and 2332401 (IV)), IR spectroscopy, and elemental analysis. According to X-ray diffraction data, the copper atoms in I–IV occur in a square pyramidal environment. The crystal packing of complexes I–III involves stacking interactions between phenanthroline molecules giving rise to supramolecular chains.

Nikiforova M.E., Kiskin M.A., Sidorov A.A., Uvarova M.A., Eremenko I.L.

The reactions of [Zn(Piv)2]n and [Gd(Piv)3]n or Gd(NO3)3∙6H2O with 2-hydroxypyridine (Hhp) or its 6-methyl derivative (Hmhp) afford heterometallic complexes [ZnGd(Рiv)5(Hhp)2]·0.5H2O (I), [Zn2Gd(Рiv)6(Hhp)2NO3]∙2C6H6 (II), [Zn3GdO(Рiv)7(Hmhp)2]∙MeCN (III), and [Zn2Gd(Рiv)6-(Hmhp)2NO3]∙0.5MeCN (IV), respectively. In the carboxylate metal cage of the synthesized complexes, the Hhp and Hmhp molecules in the form of 2-pyridone are coordinated by the metal atoms via the monodentate mode through the oxygen atoms. The introduction of Et3N into the reaction with [Zn(Рiv)2]n, Gd(NO3)3∙6H2O, and Hhp is found to result in the formation of compound [Zn4Gd2(OH)2-(Рiv)6(hp)6(Hhp)2] (V) in which the 2-hydroxypyridine anions perform the bridging function. The molecular structures of complexes I‒V are determined by XRD (CIF files CCDC nos. 2365419–2365423).

Korneeva E.V., Lutsenko I.A., Zinchenko S.V., Bekker O.B., Nelyubina Y.V., Ivanov A.V.

Shmelev M., Melnikov S., Nikolaevskii S., Kiraev S., Ananyev I., Nelyubina Y., Varaksina E., Korshunov V., Taydakov I., Goloveshkin A., Gogoleva N., Sidorov A., Eremenko I., Kiskin M.

ABSTRACTHeterometallic d‐4f coordination complexes are of paramount interest in modern coordination chemistry because of their potential applications in organic light‐emitting devices and spintronic materials. Here we report the synthesis and thorough investigation of Ln and MLn (M = Zn, Cd; Ln = Sm, Eu, Gd, Tb) molecular complexes based on 2‐furancarboxylic acid anion (Hfur): [Ln2(NO3)2(fur)4(DME)2] (Ln = Eu, Gd, Tb; DME is dimethoxyethane) and [M2Ln2(NO3)2(fur)8(bpy)2] (M = Zn, Cd; Ln = Eu, Gd, Tb, Sm; bpy is 2,2′‐bipyridyl). The structure and isostructural nature of compounds were determined based on the single‐crystal and powder X‐ray diffraction data. The photophysical properties of the obtained compounds were studied in detail: The energies of the triplet levels of the furoate anion and d‐blocks {M(fur)2(bpy)} (M = Zn, Cd), the relaxation times of the excited states, and the quantum yields were determined. Critical step from Ln complexes to ZnLn and CdLn (Ln = Eu, Tb) is accompanied by an increase in quantum yields, which correlates with a change in the energy of the triplet level of the aromatic part of the complexes and with the results of quantum chemical calculations indicating different schemes for the origination of triplet levels in MLn compounds.

Chistyakov A.S., Knyazev D.A., Zorina-Tikhonova E.N., Kiskin M.A., Vologzhanina A.V., Eremenko I.L.

Two new mixed-ligand 3d-metal (MnII, CuII) coordination compounds with diethylmalonate anions and 4,4′-bipyridine were synthesized and characterized by IR spectroscopy and X-ray diffraction. The complex [Mn(HEt2mal)2(bpy)(H2O)2]n (1) (H2Et2mal is diethylmalonic acid, bpy is 4,4′-bipyridine) contains six-coordinate metal atoms and has a chain structure. In the structure of complex 1, two interpenetrating frameworks are formed through hydrogen bonds. The coordination polymer {[Cu2(Et2mal)2(bpy)(H2O)]•6 H2O}n (2) contains four- and five-coordinate copper(ii) cations and forms infinite layers perpendicular to the crystallographic axis a.

Stabnikov P.A., Bespyatov M.A., Korolkov I.V., Sukhikh A.S., Plyusnin P.E., Trubin S.V., Sartakova A.V., Sysoev S.V.

Crystals of copper bis(heptafluorodimethyloctanedionate) (Cu(fod)2) have been grown by evaporation of solvent from solutions. Crystals of monoclinic syngony (I) have been obtained from toluene, while crystals of monoclinic (I) and triclinic (II) syngony have been obtained from acetonitrile. Crystallographic data: P21/c, a = 13.1863 (6), b = 9.8118 (4), c = 10.6997 (6), β = 113.633(2)° for I; $$\bar {1}$$ , a = 10.7941(12), b = 11.4759(14), c = 12.5263(13), α = 115.350(4)°, β = 102.957(4)°, γ = 100.999(4)° for II. Crystal packings I and II have the same structure of molecules. Crystal structures I and II are molecular and consist of discrete Cu(fod)2 molecules. Temperature dependences for saturated vapor pressure have been obtained by flow method for liquid and crystalline (phase I) Cu(fod)2 in the range 314–393 K. Thermal stability of the compound is determined, thermodynamic parameters of sublimation and evaporation have been established.

Kudryashova E.A., Valieva M.I., Slovesnova N.V., Bolotova A.V., Sayfutdinova Y.M., Vatolina S.E., Nikonov I.L., Grzhegorzhevskii K.V., Kopchuk D.S., Zyryanov G.V., Rusinov V.L.

New (bi)pyridine derivatives of the antimicrobial drug ornidazole were synthesized by alkylation of pyridyl- and 2,2′-bipyridyl-phenolic derivatives for the first time. The proposed methodology makes it possible to expand the range of ornidazole derivatives with increased antibacterial activity.

Uvarova M.A., Lutsenko I., Shmelev M., Bekker O., Lashkin A.I., Shender V.O., Nefedov S., Eremenko I.

A series of copper(II) complexes with different anions of composition [CuPhen(Hpz)2X2] (Phen = 1,10-phenanthroline; Hpz = pyrazolе; Х= CF3COO- (1), - Otf- (2), Cl- (3), Otf= CF3SO3) have been synthesized....

Koshenskova K.A., Baravikov D.E., Razvorotneva L.S., Dolgushin F.M., Bekker O.B., Khoroshilov A.V., Eremenko I.L., Lutsenko I.A.

The reactions of copper(ii) and zinc(ii) acetates with anions of 5-phenylfuran-2-carboxylic acid (Hphfur) and 5-nitro-1,10-phenanthroline (nphen) or 2,2′-bipyridine (2,2′-bpy) in the MeOH/MeCN system afforded mononuclear complexes of the composition [Cu(phfur)2(nphen)H2O] (1) and [Zn(phfur)2(2,2′-bpy)]•H2O (2). The structures of these complexes were determined by X-ray diffraction analysis (XRD). According to the XRD data, the copper atom in molecular complex 1 is in a distorted square-pyramidal environment (SQ(CuN2O3) = 0.68); the zinc atom in molecular complex 2, in a distorted trigonal-bipyramidal environment (SQ(ZnN2O3) = 3.87). The supramolecular level of 1 is mediated by intermolecular π–π interactions between the aromatic moieties of the ligands and represents a 3D supramolecular structure. in the structure of 2, the water molecules of crystallization are involved in intermolecular hydrogen bonds, resulting in the formation of centrosymmetric hydrogen-bonded dimers. The supramolecular level of 2 is mediated by C—H⋯O and C—H⋯π interactions. According to the simultaneous thermal analysis, complexes 1 and 2 are characterized by different types of thermal destruction. Thus, the explosophoric groups in the ligands of compound 1 are responsible for an intense exothermic effect. The results of biological assays show a certain correlation between the type of the substituted moiety in the heterocycle and the activity against the non-pathogenic Mycolicibacterium smegmatis strain.

Koshenskova K.A., Baravikov D.E., Kayukova L.A., Ergalieva E.M., Nelyubina Y.V., Nikiforova M.E., Dolgushin F.M., Fedin M.V., Bekker O.B., Shender V.O., Malyants I.K., Aliev T.M., Titov K.O., Eremenko I.L., Lutsenko I.A.

Two cationic and molecular copper(II) complexes - mixed ligand [{Cu(phen)2benz}{Cu(phen)2Cl}]2+·2Cl-·benz-·H3O+·4·.5H2O (1), [Cu(benz)2phen] (2) (benz- = m-Cl-benzoate anion; phen = 1,10-phenantroline) and [Cu(phen)3]2+·2OTf-·2EtOH (3) (OTf = trifluoromethylsulfonate, triflate anion, CF3SO3-) were synthesized using various synthetic approaches and thoroughly characterized by spectroscopic methods and single crystal X-ray diffraction analysis. The structures of the complexes according to X-ray diffraction data are characterized by a diverse geometric environment of the complexing agent - the cationic form of 1 comprises two structurally nonequivalent moieties: the Cu (1) and Cu (2) complex-forming atoms coordinate, in chelate manner, two phen moieties each and the benz- (1)/Cl- (2) anions, respectively, thus forming different-ligand formula units, a trigonal–bipyramidal {Cu(1)N4Cl} and a pseudo octahedral one {Cu(2)N4O2}. The copper(II) ion in the complex 2 coordinates one phen ligand in a bidentate mode and two benz- anions to produce a distorted planar square environment {CuN2O2}. In complex 3, the copper(II) cation is surrounded by three phenanthroline fragments {Cu(phen)3}2+ and non-coordinated OTf- ions. The results of an EPR study 1 show that in the solid phase, intermolecular exchange interactions that cause exchange narrowing of the spectrum are efficient, whereas in solutions, resolved spectra of copper(II) ion with rhombic symmetry of the g-tensor are observed. An in vitro study of the biological properties of 1–3 toward nonpathogenic mycobacterial strain Mycolicibacterium smegmatis showed an increase in biological effectiveness depending on the structure of complexes (MIC, 1 (2 nmol/disk) > 3 (5 nmol/disk) > 2 (12.5 nmol/disk)). Complex 1 was also tested for antitumor activity against an ovarian adenocarcinoma SKOV3 demonstrated high efficiency: the IC50 value is almost 9 times higher than the activity of cisplatin.

Klarek M., Kowalski K.

Article summarizes over 12 years of studies on organometallic nucleic acid components in our laboratory. It outlines synthetic chemistry, redox, photophysical and biological properties alike. It also shows directions for future development.

Uvarova M.A., Lutsenko I., Shmelev M., Bekker O., Lashkin A.I., Shender V.O., Nefedov S., Eremenko I.

A series of copper(II) complexes with different anions of composition [CuPhen(Hpz)2X2] (Phen = 1,10-phenanthroline; Hpz = pyrazolе; Х= CF3COO- (1), - Otf- (2), Cl- (3), Otf= CF3SO3) have been synthesized....

Koshenskova K.A., Baravikov D.E., Kayukova L.A., Ergalieva E.M., Nelyubina Y.V., Nikiforova M.E., Dolgushin F.M., Fedin M.V., Bekker O.B., Shender V.O., Malyants I.K., Aliev T.M., Titov K.O., Eremenko I.L., Lutsenko I.A.

Two cationic and molecular copper(II) complexes - mixed ligand [{Cu(phen)2benz}{Cu(phen)2Cl}]2+·2Cl-·benz-·H3O+·4·.5H2O (1), [Cu(benz)2phen] (2) (benz- = m-Cl-benzoate anion; phen = 1,10-phenantroline) and [Cu(phen)3]2+·2OTf-·2EtOH (3) (OTf = trifluoromethylsulfonate, triflate anion, CF3SO3-) were synthesized using various synthetic approaches and thoroughly characterized by spectroscopic methods and single crystal X-ray diffraction analysis. The structures of the complexes according to X-ray diffraction data are characterized by a diverse geometric environment of the complexing agent - the cationic form of 1 comprises two structurally nonequivalent moieties: the Cu (1) and Cu (2) complex-forming atoms coordinate, in chelate manner, two phen moieties each and the benz- (1)/Cl- (2) anions, respectively, thus forming different-ligand formula units, a trigonal–bipyramidal {Cu(1)N4Cl} and a pseudo octahedral one {Cu(2)N4O2}. The copper(II) ion in the complex 2 coordinates one phen ligand in a bidentate mode and two benz- anions to produce a distorted planar square environment {CuN2O2}. In complex 3, the copper(II) cation is surrounded by three phenanthroline fragments {Cu(phen)3}2+ and non-coordinated OTf- ions. The results of an EPR study 1 show that in the solid phase, intermolecular exchange interactions that cause exchange narrowing of the spectrum are efficient, whereas in solutions, resolved spectra of copper(II) ion with rhombic symmetry of the g-tensor are observed. An in vitro study of the biological properties of 1–3 toward nonpathogenic mycobacterial strain Mycolicibacterium smegmatis showed an increase in biological effectiveness depending on the structure of complexes (MIC, 1 (2 nmol/disk) > 3 (5 nmol/disk) > 2 (12.5 nmol/disk)). Complex 1 was also tested for antitumor activity against an ovarian adenocarcinoma SKOV3 demonstrated high efficiency: the IC50 value is almost 9 times higher than the activity of cisplatin.

Kostova I.

Abstract: Metal-based coordination compounds have very special place in bioinorganic chemistry because of their different structural arrangements and significant application in medicine. Rapid progress in this field increasingly enables the targeted design and synthesis of metal-based pharmaceutical agents that fulfill valuable roles as diagnostic or therapeutic agents. Various coordination compounds have important biological functions, both those initially present in the body (endogenous) and those entering the organisms from the external environment (exogenous): vitamins, drugs, toxic substances, etc. In the therapeutic and diagnostic practice, both the essential for all living organisms and the trace metals are used in metal-containing coordination compounds. In the current review, the most important functional biologically active compounds were classified group by group according to the position of the elements in the periodic table.

Koshenskova K.A., Makarenko N.V., Baravikov D.E., Dolgushin F.M., Bekker O.B., Eremenko I.L., Lutsenko I.A.

The reactions in the Cu(OAc)2⋅H2O–phytic acid–2,2'-bipyridine (bpy) system in aqueous methanol solutions resulted in the formation of a molecular different-ligand tetranuclear complex [(Cu4(bpy)4(PO4)2(CO3)(H2O)2]⋅13H2O (I), the structure of which was established from the X-ray diffraction data (CCDC no. 2262998). The molecule of complex I contains four non-equivalent Cu2+ cations, coordinating each two phosphate anions ( $${\text{PO}}_{4}^{{3 - }}$$ remaining after the transformation of the phytate ring), four neutral bpy molecules, two water molecules, and one carbonate anion ( $${\text{CO}}_{3}^{{2 - }}$$ ). The presence of a large number of solvate water molecules in the outer coordination sphere gives rise to a hydrogen-bonded framework involved in stabilization of the crystal packing. Study of the antimycobacterial activity of I against non-pathogenic Mycolicibacterium smegmatis strain revealed high biological efficacy.

Endale H., Mathewos M., Abdeta D.

Abhijnakrishna R., Magesh K., Ayushi A., Velmathi S.

The compound 2,2′;6,2″ terpyridine has attracted significant interest in the fields of supramolecular chemistry, materials science, and coordination chemistry due to its unique properties, including intense non-radiative relaxation and low quantum yields. With its tridentate ligand capabilities stemming from three nitrogen atoms, terpyridine ligands have been extensively studied, particularly the 4′-functionalized variants. These ligands exhibit strong chelating and binding abilities towards various transition and rare earth metals, making them valuable in electrochemistry, biochemistry, and photophysical chemistry. However, their biological activity is the most intriguing aspect of metal-terpyridine complexes. These complexes have shown tremendous potential in biological systems, acting as anti-tumour and cell imaging agents. Their exceptional binding properties enable interactions with vital biological targets such as DNA, proteins, and enzymes, offering promising avenues for therapeutic interventions. Additionally, these complexes have proven to be effective sensors capable of recognizing biologically essential anions and amino acids. While numerous review articles have been published on metal-terpyridine complexes and their applications, there has been a notable gap in the literature since 2012, specifically focusing on the biological activity of these complexes. Hence, there is a need for an in-depth review article that explores the advancements in the biological activity of metal-terpyridine complexes over the past decade. Such a comprehensive overview would provide researchers in this field with valuable insights into the intricate interplay between terpyridine ligands and metal ions, shedding light on their potential for therapeutic applications and inspiring further investigations in this exciting area of research.

Aguilar-Jiménez Z., Espinoza-Guillén A., Resendiz-Acevedo K., Fuentes-Noriega I., Mejía C., Ruiz-Azuara L.

In this review, we present a timeline that shows the origin of mixed chelate copper (II) complexes, registered as Mark Title Casiopeínas®, as the first copper (II) compounds proposed as anticancer drugs in 1988 and 1992. In the late twentieth century, the use of essential metals as anticancer agents was not even considered, except for their antifungal or antibacterial effects; also, copper, as gold salts, was used for arthritis problems. The use of essential metals as anticancer drugs to diminish the secondary toxic effects of Cisplatin was our driving force: to find less toxic and even more economical compounds under the rational design of metal chelate complexes. Due to their chemical properties, copper compounds were the choice to continue anticancer drug development. In this order of ideas, the rational designs of mixed chelate–copper (II) complexes (Casiopeínas, (Cas) homoleptic or heteroleptic, depending on the nature of the secondary ligand) were synthesized and fully characterized. In the search for new, more effective, and less toxic drugs, Casiopeína® (Cas) emerged as a family of approximately 100 compounds synthesized from coordinated Cu(II) complexes with proven antineoplastic potential through cytotoxic action. The Cas have the general formula [Cu(N–N)(N–O)]NO3 and [Cu(N–N)(O–O)]NO3, where N–N is an aromatic substituted diimine (1,10-phenanthroline or 2,2′-bipyridine), and the oxygen donor (O–O) is acetylacetonate or salicylaldehyde. Lately, some similar compounds have been developed by other research groups considering a similar hypothesis after Casiopeína’s discoveries had been published, as described herein. As an example of translational medicine criteria, we have covered each step of the established normative process for drug development, and consequently, one of the molecules (Casiopeína III ia (CasIIIia)) has reached the clinical phase I. For these copper compounds, other activities, such as antibacterial, antiparasitic and antiviral, have been discovered.

Koshenskova K.A., Baravikov D.E., Nelyubina Y.V., Primakov P.V., Shender V.O., Maljants I.K., Bekker O.B., Aliev T.M., Borodin E.A., Kotel’nikov D.D., Leusova N.Y., Mantrov S.N., Kiskin M.A., Eremenko I.L., Lutsenko I.A.

The reaction of copper(II) acetate with 2-furancarboxylic (HFur)/5-nitro-2-furancarboxylic (HNfur) acids and 5-nitro-1,10-phenanthroline (Nphen) in methanol resulted in the formation of the binuclear coordination compounds [Cu2(L)4(Nphen)2]·X (L = Fur (I), Nfur (II); X = H2O (I)), which were structurally studied by direct X-ray diffraction (CCDC no. 2244205 (I) and 2244206 (II)). According to X-ray diffraction data, the coordination environment of the central metal ion in I and II is composed of two nitrogen atoms of Nphen and three oxygen atoms of the acid anions, which thus form the {CuN2O3} tetragonal pyramid in which the copper coordination number is five. Intermolecular hydrogen bonds and stacking interactions between the Nphen aromatic rings provide supramolecular stabilization of I and II. A characteristic feature of supramolecular organization of II is the presence of a coordination bond between the Cu2+ cation and oxygen of the Nphen $${\text{NO}}_{2}^{ - }$$ group of parallel chains. A biological activity assay for complexes I and II concerning the cytotoxic properties against a human ovarian adenocarcinoma cell line (SKOV3) and the mycobacterial strain Mycolicibacterium smegmatis showed an efficient suppression of cell viability. The results of mathematical modeling of the probability of Cu2+ binding to amino acid residues of M. smegmatis proteins suggested the affinity of the Cu(II) ion to a number of amino acids in polypeptide sites. It was shown that metal ion binding in mycobacterial proteins is more characteristic of histidine- and glutamic acid-containing moieties.

Uvarova M.A., Novikova M.V., Eliseenkova V.A., Baravikov D.E., Dolgushin F.M., Bekker O.B., Fatushina E.V., Kiskin M.A., Eremenko I.L., Lutsenko I.A.

The reaction of copper(II) and zinc(II) acetates with 3-furancarboxylic (HFur) and 2-thiophenecarboxylic (HTph) acids with subsequent addition of 3,5-dimethylpyrazole (HDmpz) gave mononuclear complexes [M(L)2(HDmpz)2] (M = Cu(II), L = Fur– (I), Tph– (II); Zn(II), L = Fur– (III)). The structures of compounds I–III were determined by X-ray diffraction. According to X-ray diffraction data, I and II are isostructural: the central Cu(II) atom occurs in a square planar environment formed by two oxygen atoms of carboxylate anions and HDmpz nitrogen atoms; in III, the Zn atom is in the tetrahedral environment of two furoate anions and HDmpz molecules, thus forming the {MO2N2} groups. The complexes are additionally stabilized in the crystal by inter- (I and II) and intramolecular (III) hydrogen bonds. The biological activity of I–III was determined in relation to the non-pathogenic Mycolicibacterium smegmatis.

Belinskaia D.A., Jenkins R.O., Goncharov N.V.

Being one of the main proteins in the human body and many animal species, albumin plays a decisive role in the transport of various ions, electrically neutral molecules and in maintaining the colloid osmotic pressure of the blood [...]

Nikiforova M.E., Yambulatov D.S., Nelyubina Y.V., Primakov P.V., Bekker O.B., Majorov K.B., Shmelev M.A., Khoroshilov A.V., Eremenko I.L., Lutsenko I.A.

The interaction of Mg2+ with 2-furoic acid (HFur) and oligopyridines, depending on the synthesis conditions, leads to the formation of mixed-ligand complexes [Mg(H2O)4(phen)]·2HFur·phen·H2O (1), [Mg(NO3)2(phen)2] (2) and [Mg3(Fur)6(bpy)2]·3CH3CN (3); these structures were determined with an SC X-ray analysis. According to the X-ray diffraction data, in complex 1, obtained in ambient conditions, the magnesium cation coordinated four water molecules and one phenanthroline fragment, while in complexes 2 and 3 (synthesized in an inert atmosphere), the ligand environment of the complexing agent was represented by neutral oligopyridine molecules and acid anions. The thermal behavior of 1 and 2 was studied using a simultaneous thermal analysis (STA). The in vitro biological activity of complexes 1–3 was studied in relation to the non-pathogenic Mycolicibacterium smegmatis and the virulent strain Mycobacterium tuberculosis H37Rv.

Koshenskova K.A., Baravikov D.E., Khoroshilov A.V., Nelyubina Y.V., Primakov P.V., Bekker O.B., Dokuchaeva K.S., Dolgushin F.M., Kiskin M.A., Eremenko I.L., Lutsenko I.A.

Polymer complexes of the composition {[Cu2(fur)4(bpy)]n • nMeOH} (1) and {[Ag3(fur)(bpy)4]n•2nfur·13.5nH2O} (2) were synthesized by the reactions of copper(ii) and silver(i) acetates, respectively, with anions of furancarboxylic acid (Hfur) and 4,4’-bi-pyridine (bpy) under different synthesis conditions. The structures of the new complexes were established by X-ray diffraction (XRD) analysis. According to the XRD data, complex 1 is a polymer, in which the molecular metal oxide moieties are connected in a monodentate manner through bpy to form a 1D structural motif. The coordination environment of the copper(ii) atom in complex 1 can be described as a square pyramid {CuO4N}; the coordination number is 5. ionic complex 2 contains three nonequivalent Agi atoms in different coordination environment with different coordination numbers of the complexing metal (CNAg(1) = 4; CNAg(2)Ag(3) = 2). The supramolecular level of complex 2 is a 3D structure stabilized by different types of interactions, such as hydrogen bonds, π-stacking and ar-gentophilic interactions. The simultaneous thermal analysis demonstrated that complex 1 undergoes desolvation and decarboxylation at temperatures below 234 °C, whereas the bipyridine moieties coordinated to the copper(ii) atoms are not completely eliminated even at 500 °C. The in vitro biological activity of complexes 1 and 2 was evaluated against the non-pathogenic mycobacterial strain Mycolicibacterium smegmatis.

Nebykov D.N., Razvalyaeva A.V., Panov A.O., Latyshova S.E., Mokhov V.M.

Climova A., Pivovarova E., Szczesio M., Gobis K., Ziembicka D., Korga-Plewko A., Kubik J., Iwan M., Antos-Bielska M., Krzyżowska M., Czylkowska A.

In this study, three new organic ligands N'-(benzylidene)-6-chloropyrazine-2-carbohydrazonamide (L1), 6-chloro-N'-(4-nitrobenzylidene)picolinohydrazonamide(L2), and N'-(benzylidene)-4-chloropicolinohydrazonamide (L3) and three copper coordination compounds (Cu(L1)Cl2, Cu(L2)Cl2 and Cu(L3)Cl2) based on them were synthesized. All obtained compounds were characterized using appropriate analytical techniques: elemental analysis (EA), thermogravimetric analysis (TG-DTG), Fourier transform infrared spectroscopy (FTIR) and flame-atomic absorption spectrometry (F-AAS). These methods of physicochemical analyses helped to assume that the complexation in three cases proceeds in a bidentate manner. The X-ray investigation confirmed the synthesis pathway and molecular structures for L1 and L3 ligands. The antimicrobial activity of the obtained compounds was then comprehensively investigated, where Cu(L3)Cl2 showed the strongest antibacterial properties against all tested bacteria (Pseudomonas aeruginosa, Staphylococcus aureus, Escherichia coli). LN229 human glioma cells and BJ human normal fibroblasts cells were treated with tested compounds and their cytotoxicity was evaluated with MTT test. The effect of complexing on antitumor activity has been investigated. The ligand L1 and its complex showed similar activity against normal cells while complexation increases toxicity against cancer cells in concentrations of 50 and 100 μM. For the one pair of ligand/complex compounds the apoptosis detection, cell cycle analysis and gene expression analysis (qRT-PCR) were performed. Cu(L1)Cl2 showed the stronger toxic effect in comparison with L1 due to the population of early apoptotic cells which revealed metabolic activity in MTT assay.