Synthesis, crystal structure, potential drug properties for Coronavirus of Co(II) and Zn(II) 2-chlorobenzoate with 3-cyanopyridine complexes.

Two new complexes of Co(II) and Zn(II) 2-chlorobenzoate (2-ClBA) with 3-cyanopyridine (CNP) of the general formula [Co(2-ClBA)2(CNP)2(H2O)2] and [Zn(2-ClBA)2(CNP)2(H2O)2] were synthesized. The structures of the complexes were characterized by single crystal XRD and FT-IR and NMR spectroscopy and Mass Spectrometry (MALDI-TOF MS) methods. Mononuclear complexes exhibit octahedral coordination. In addition, Hirshfeld surface analysis was performed to determine non-covalent interactions in crystal packing. The geometry optimization of the molecules was carried out using the LANL2DZ level of theory of the DFT method and the obtained findings were confirmed by comparing with the data obtained from the single crystal X-ray diffraction method. The theoretical and experimental bond angles and lengths are very close to each other. The effectiveness of the complexes against SARS-CoV-2 enzymes was investigated in silico using the molecular docking method, and a binding score of -8.0 kcal/mol on NSP16 of complex 1 as an inhibitor was obtained. To investigate the drug potential of the complexes, their pharmacokinetic and toxicokinetic properties were estimated by ADMET calculations.

Synthesis and Crystallographic, Absorption and Emission Studies of 4-Pyridine Carboxamide of Zn(II) 4-Chlorophenylacetate.

A new zinc(II) complex, [Zn(CB)2(INA)2] (where CB is 4-chlorophenylacetate and INA is 4-pyridine carboxamide) was synthesized. The structure of the complex was characterized by elemental analysis, FT-IR spectroscopy and single-crystal X-ray diffraction technique. Besides, the thermal stability of the complex was investigated by TGA/DTA analysis method. Moreover, the optical absorption and the emission features of the complex were examined by using UV-Vis and fluorescence spectrophotometers, respectively. Furthermore, Density Functional Theory (DFT) calculations were carried out to support the experimental results. Accordingly, it was determined that the complex crystallized in a monoclinic system with space group Pc, a = 8.3329 (2) Å, b = 25.6530 (4) Å, c = 13.5048 (3) Å, α = 90°, ß = 91.703 (3)° and γ = 90°. The complex consists two crystallographically independent molecules. In each molecule, the ZnII ion adopts a distorted trigonal pyramidal coordination formed by two O atoms from the two 4 chlorophenylacetate ligand and two N atoms of the two 4-pyridine carboxamide ligands. It was observed that the linear absorption spectra of the complex were similar to linear absorption spectra of the semiconductors. In addition, two emission peaks were observed in the fluorescence spectra which could be due to the formation of excimer and the interactions of the benzene and pyridine rings. The energy gap (ΔEgap = ELUMO - EHOMO) of the complex has been calculated as 3.712 eV and this value is very close to the experimentally measured value (3.86 eV). Therefore, because of higher fluorescence intensity of emission peak that was observed between 309 and 556 nm wavelength besides other traits, the complex could potentially be used in the blue light OLED application by filtering of the emission peak around 710 nm wavelength. Graphical Abstract It was reported synthesis and spectroscopic, structural and optical characterization of a new complex that is Zn(II) of 4-Chlorophenylacetate with isonicotinamide. The complex characterized by elemental analysis, Single crystal X-ray diffraction and FT-IR Spectroscopy. Thermal stabilities of the complex have also been investigated. The studying of the optical absorption and fluorescence spectra of the prepared complex is very important for the determination of the optical application areas. The fluorescence measurements showed that these materials are much suitable for application area of the detection of nitroaromatic explosives. In addition to the Density Functional Theory (DFT) calculations were carried out to support the experimental results. It was reported synthesis and spectroscopic, structural and optical characterization of a new complex that is Zn(II) of 4-Chlorophenylacetate with isonicotinamide. The complex characterized by elemental analysis, Single crystal X-ray diffraction and FT-IR Spectroscopy. Thermal stabilities of the complex have also been investigated. The studying of the optical absorption and fluorescence spectra of the prepared complex is very important for the determination of the optical application areas. In addition to the Density Functional Theory (DFT) calculations were carried out to support the experimental results.

Crystal structure and Hirshfeld surface analysis of hexa-kis-(µ-benzoato-κ2O:O')bis-(pyridine-3-carbo-nitrile-κN1)trizinc(II).

The asymmetric unit of the title complex, [Zn3(C7H5O2)6(C6H4N2)2], contains one half of the complex mol-ecule, i.e. one and a half ZnII cations, three benzoate (Bnz) and one pyridine-3-carbo-nitrile (Cpy) mol-ecule; the Bnz anions act as bidentate ligands through the carboxyl-ate O atoms, while the Cpy ligand acts as a monodentate N(pyridine)-bonding ligand. The complete centrosymmetric trinuclear complex thus comprises a linear array of three ZnII cations. The central ZnII cation shows an octa-hedral coordination and is bridged to each of the terminal ZnII cations by three Bnz anions. By additional coordination of the CPy ligand, the terminal ZnII cations adopt a trigonal-pyramidal coordination environment. In the crystal, the Bnz anions link to the Cpy N atoms via weak C-H⋯N hydrogen bonds, forming a two-dimensional network. C-H⋯π and π-π inter-actions [between the benzene and pyridine rings of adjacent mol-ecules with an inter-centroid distance of 3.850 (4) Å] help to consolidate a three-dimensional architecture. The Hirshfeld surface analysis confirms the role of H-atom contacts in establishing the packing.

Crystal structure of trans-di-aqua-bis-(4-cyano-benzoato-κO)bis-(N,N-di-ethyl-nicotinamide-κN)cadmium.

The mononuclear title cadmium complex, [Cd(C10H14N2O)2(C8H4NO2)2(H2O)2], is centrosymmetric and contains two water mol-ecules, two 4-cyanobenzoate (CB) ligands and two di-ethyl-nicotinamide (DENA) ligands. All the ligands are coordinated to the CdII atom in a monodentate mode. The four nearest O atoms around the CdII atom form a slightly distorted square-planar arrangement, with the distorted octa-hedral coordination sphere being completed by the two pyridine N atoms of the DENA ligands at distances of 2.3336 (13) Å. The dihedral angle between the carboxyl-ate group and the adjacent benzene ring is 8.75 (16)°, while the benzene and pyridine rings are oriented at a dihedral angle of 57.83 (5)°. The water mol-ecules exhibit both intra-molecular [to the non-coordinating carboxyl-ate O atom, enclosing an S(6) hydrogen-bonding motif, where O⋯O = 2.670 (2) Å] and inter-molecular [to the amide carbonyl O atom, enclosing an R22(16) ring motif, where O⋯O = 2.781 (2) Å] O-H⋯O hydrogen bonds. The latter lead to the formation of supra-molecular chains propagating along [110].

The Therapeutic Role of Glutathione in Oxidative Stress and Oxidative DNA Damage Caused by Hexavalent Chromium.

Hexavalent chromium Cr (VI) causes various toxic and carcinogenic effects. The main carcinogenic effect is observed in the pulmonary system through inhalation route. Reduction of Cr (VI) to Cr (V, IV, and III) reactive intermediates within the cells by intracellular reducing agents such as glutathione is an important event leading to oxidative stress and oxidative DNA damage. This study evaluated the effects of intraperitoneal administration of Cr (VI) and GSH on total oxidant status (TOS), total antioxidant capacity (TAC), oxidative stress index, and oxidative DNA damage by evaluating the level of 8-hydroxy-2́-deoxyguanosine (8-OHdG) in Swiss-Albino mice. Seventy two mice were divided into 6 groups and treated intraperitoneally as follow: control (saline), group GSH (30 mg/kg GSH) groups of Cr-20 (20 mg/kg, K2Cr2O7), Cr-30 (30 mg/kg K2Cr2O7), Cr-20 + GSH (20 mg/kg K2Cr2O7 + 30 mg/kg GSH), Cr-30 + GSH (30 mg/kg K2Cr2O7 + 30 mg/kg GSH). Total oxidant capacities of Cr-20 and Cr-30 were increased compared to control, Cr-20 + GSH, and Cr-30 + GSH. TOS levels in Cr-20 + GSH and Cr-30 + GSH were lower than in Cr-20 and Cr-30. No difference in TAC was observed among the groups. 8-Hydroxy-2́-deoxyguanosine levels were increased in groups Cr-20 and Cr-30 compared with control and groups Cr-20 + GSH and Cr-30 + GSH. No difference was determined in 8-OHdG levels among control, groups GSH, Cr-20 + GSH and Cr-30 + GSH. Results indicate that Cr (VI) given i.p. route causes increased oxidative stress and oxidative DNA damage in the blood of Swiss-Albino mice. Administration of GSH via i.p. route protects from oxidative stress and DNA damage.

Bis(µ-4-formyl-benzoato-κ(2) O:O')bis-[(4-formyl-benzoato-κ(2) O,O')bis-(iso-nicotin-amide-κN (1))copper(II)].

The asymmetric unit of the centrosymmetric dinuclear title compound, [Cu2(C8H5O3)4(C6H6N2O)4], contains one half of the complex mol-ecule. The Cu(II) atoms are bridged by the carboxyl-ate groups of two 4-formyl-benzoate (FOB) anions. Besides the two bridging FOB anions, one additional chelating FOB anion and two isonicotinamide (INA) ligands complete the distorted CuN2O4 octa-hedral coordination of each Cu(2+) cation. Within the asymmetric unit, the benzene and pyridine rings are oriented at dihedral angles of 25.1 (3) and 12.6 (3)°, respectively. In the crystal, N-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network. π-π contacts between the pyridine rings [shortest centroid-centroid distance = 3.821 (3) Å] may further stabilize the crystal structure. One of the formyl groups of the two FOB anions is disordered over two sets of sites with an occupancy ratio of 0.65:0.35.

Poly[(µ(5)-2,2'-bipyridine-5,5'-dicarboxyl-ato)lead(II)].

In the title polymeric compound, [Pb(C(12)H(6)N(2)O(4))](n), the Pb(II) cation, located on a mirror plane, is N,N'-chelated by a 2-2'-bipyridine-5,5'-dicarboxyl-ate (bpdc) anion and is further coordinated by six O atoms from four carboxyl groups of bpdc anions in an irregular N(2)O(6) geometry. The carboxylate groups bridge the Pb(II) cations, forming a three-dimensional polymeric structure. The carboxyl-ate group is twisted away from the attached pyridine ring by 11.4 (3)°.

Diaqua-bis-(N,N-diethyl-nicotinamide-κN(1))bis-(4-formyl-benzoato-κO(1))zinc.

In the title complex, [Zn(C(8)H(5)O(3))(2)(C(10)H(14)N(2)O)(2)(H(2)O)(2)], the Zn(II) cation is located on an inversion center and is coordinated by two 4-formyl-benzoate anions, two N,N-diethyl-nicotinamide (DENA) ligands and two water mol-ecules. The four O atoms in the equatorial plane around the Zn(II) cation form a slightly distorted square-planar arrangement, while the slightly distorted octa-hedral coordination is completed by the two N atoms of the DENA ligands in the axial positions. The dihedral angle between the carboxyl-ate group and the adjacent benzene ring is 2.96 (11)°, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 79.26 (4)°. The coordinating water mol-ecule links with the carboxyl-ate group via an intra-molecular O-H⋯O hydrogen bond. In the crystal, O-H⋯O and weak C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional supra-molecular network. A π-π contact between the parallel pyridine rings of adjacent mol-ecules may further stabilize the crystal structure [centroid-centroid distance = 3.5654 (8) Å].

Diaqua-bis-(4-formyl-benzoato-κO(1))bis-(nicotinamide-κN(1))cobalt(II).

In the title complex, [Co(C(8)H(5)O(3))(2)(C(6)H(6)N(2)O)(2)(H(2)O)(2)], the Co(II) cation is located on an inversion center and is coordinated by two 4-formyl-benzoate (FB) anions, two nicotinamide (NA) ligands and two water mol-ecules. The four O atoms in the equatorial plane around the Co(II) cation form a slightly distorted square-planar arrangement, while the slightly distorted octa-hedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl-ate group and the adjacent benzene ring is 23.91 (9)°, while the pyridine and benzene rings are oriented at a dihedral angle of 88.84 (4)°. The coordinating water mol-ecule links with the carboxyl-ate group via an intra-molecular O-H⋯O hydrogen bond. In the crystal, N-H⋯O, O-H⋯O and weak C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional supra-molecular network. π-π stacking between the parallel benzene rings of adjacent mol-ecules [centroid-centroid distance = 3.8505 (8) Å] may further stabilize the structure. A weak C-H⋯π inter-action also occurs in the crystal.

Diaqua-bis-(4-formyl-benzoato-κO(1))bis-(nicotinamide-κN(1))zinc.

In the title complex, [Zn(C(8)H(5)O(3))(2)(C(6)H(6)N(2)O)(2)(H(2)O)(2)], the Zn(II) cation is located on an inversion center and is coordinated by two 4-formyl-benzoate (FB) anions, two nicotinamide (NA) ligands and two water mol-ecules. The four O atoms in the equatorial plane around the Zn(II) cation form a slightly distorted square-planar arrangement, while the slightly distorted octa-hedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl-ate group and the adjacent benzene ring is 24.13 (8)°, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 88.52 (4)°. The coordinating water mol-ecule links with the carboxyl-ate group via an O-H⋯O hydrogen bond. In the crystal, N-H⋯O and O-H⋯O hydrogen bonds, and a weak C-H⋯π inter-action link the mol-ecules into a two-dimensional network parallel to (010). These networks are linked via C-H⋯O and π-π inter-actions between inversion-related benzene rings [centroid-centroid distance = 3.8483 (7) Å], forming a three-dimensional supra-molecular structure.

Diaqua-bis-(4-formyl-benzoato-κO(1))bis-(nicotinamide-κN(1))copper(II).

In the title complex, [Cu(C(8)H(5)O(3))(2)(C(6)H(6)N(2)O)(2)(H(2)O)(2)], the Cu(II) cation is located on an inversion center and is coordinated by two 4-formyl-benzoate (FB) anions, two nicotinamide (NA) ligands and two water mol-ecules in an elongated distorted octa-hedral geometry. The dihedral angle between the carboxyl-ate group and the adjacent benzene ring is 23.00 (10)°, while the pyridine ring and the benzene ring are oriented at a dihedral angle of 85.34 (4)°. An intra-molecular O-H⋯O hydrogen bond occurs between coordinating water mol-ecule and the carboxyl-ate group. In the crystal, N-H⋯O, O-H⋯O and weak C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional supra-molecular network. A weak C-H⋯π inter-action also occurs in the crystal.

Diaqua-bis-(4-formyl-benzoato-κO(1))bis-(nicotinamide-κN(1))nickel(II).

In the title complex, [Ni(C(8)H(5)O(3))(2)(C(6)H(6)N(2)O)(2)(H(2)O)(2)], the Ni(II) cation is located on an inversion center and is coordinated by two 4-formyl-benzoate (FB) anions, two nicotinamide (NA) ligands and two water mol-ecules. The four O atoms in the equatorial plane around the Ni(II) cation form a slightly distorted square-planar arrangement, while the slightly distorted octa-hedral coordination is completed by the two N atoms of the NA ligands in the axial positions. The dihedral angle between the carboxyl-ate group and the adjacent benzene ring is 23.67 (8)°, while the pyridine and benzene rings are oriented at an angle of 89.04 (4)°. The coordinating water mol-ecule links with the carboxyl-ate group via an O-H⋯O hydrogen bond. In the crystal, N-H⋯O, O-H⋯O and weak C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional supra-molecular network. π-π contacts between benzene rings [centroid-centroid distance = 3.8414 (7) Å] may further stabilize the structure. A weak C-H⋯π inter-action also occurs.

Tetra-aqua-bis(isonicotinamide-κN)cobalt(II) bis-(4-formyl-benzoate) dihydrate.

The asymmetric unit of the crystal structure of the title complex, [Co(C(6)H(6)N(2)O)(2)(H(2)O)(4)](C(8)H(5)O(3))(2)·2H(2)O, contains one-half of the complex cation with the Co(II) ion located on an inversion center, a 4-formyl-benzoate (FB) counter-anion and an uncoordinated water mol-ecule. The four O atoms in the equatorial plane around the Co(II) ion form a slightly distorted square-planar arrangement with an average Co-O bond length of 2.086 Å; the slightly distorted octa-hedral coordination is completed by the two N atoms of the isonicotinamide (INA) ligands at a slightly longer distance [2.1603 (14) Å] in the axial positions. The dihedral angle between the carboxyl-ate group and the attached benzene ring is 5.93 (13)°, while the pyridine and benzene rings are oriented at a dihedral angle of 3.09 (6)°. In the crystal structure, O-H⋯O, N-H⋯O and C-H⋯O hydrogen bonds link the mol-ecules into a three-dimensional network. π-π Contacts between the benzene and pyridine rings [centroid-centroid distance = 3.758 (1) Å] may further stabilize the crystal structure.

catena-Poly[[(4-formyl-benzoato-κO)(isonicotinamide-κN)zinc(II)]-µ-4-formyl-benzoato-κO:O].

In the title compound, [Zn(C(8)H(5)O(3))(2)(C(6)H(6)N(2)O)](n), the Zn(II) ion is tetrahedrally coordinated by two formyl-benzoate (FB) and one isonicotinamide (INA) ligands while symmetry-related FB ligands bridge adjacent Zn(II) ions, forming polymeric chains along the b axis. The carboxyl-ate groups in the two FB ions are twisted away from the attached benzene ring by 9.07 (2) and 26.2 (2)°. The two benzene rings of the FB ions are oriented at a dihedral angle of 81.30 (5)°. In the crystal, adjacent polymeric chains inter-act via N-H⋯O and C-H⋯O hydrogen bonds, π-π contacts between the formyl-benzoate rings [centroid-centroid distance = 3.7736 (8) Å] and weak C-H⋯π inter-actions, forming a three-dimensional network.

Diaqua-bis(N,N-diethyl-nicotinamide-κN)bis-(4-formyl-benzoato-κO)manganese(II).

The title compound, [Mn(C(8)H(5)O(3))(2)(C(10)H(14)N(2)O)(2)(H(2)O)(2)], contains one Mn(II) atom lying on an inversion centre, two 4-formyl-benzoate and two diethyl-nicotinamide ligands and two coordinated water mol-ecules. All ligands are monodentate. The four O atoms around the Mn atom form a slightly distorted equatorial plane, while the distorted octa-hedral coordination is completed by the two N atoms in the axial positions. An intra-molecular O-H⋯O hydrogen bond occurs in the complex. In the crystal structure, O-H⋯O hydrogen bonds link the mol-ecules through an R(2) (2)(16) ring motif, forming a one-dimensional chain along the a axis. The π-π contact between the pyridyl rings [centroid-centroid distance = 3.629 (2) Å] may further stabilize the structure.

Diaqua-bis(N,N-diethyl-nicotinamide-κN)bis-(4-formyl-benzoato-κO)nickel(II).

In the title centrosymmetric mononuclear Ni(II) compound, [Ni(C(8)H(5)O(3))(2)(C(10)H(14)N(2)O)(2)(H(2)O)(2)], the central Ni(II) atom is coordinated by two O atoms from two 4-formyl-benzoate (FOB) ligands, two O atoms from two water mol-ecules and two N atoms from two diethyl-nicotinamide (DENA) ligands. The coordination geometry is slightly distorted octa-hedral, with four O atoms in the equatorial plane and two N atoms in axial positions. Intra-molecular O-H⋯O hydrogen bonds are observed. In the crystal structure, mol-ecules are linked into chains along the a axis by inter-molecular O-H⋯O hydrogen bonds. The structure is further stabilized by π-π inter-actions between the pyridine rings of DENA units, with a centroid-centroid distance of 3.668 (2) Å.

Diaqua-bis(N,N-diethyl-nicotinamide-κN)bis-(4-formyl-benzoato-κO)cobalt(II).

In the crystal structure of the title Co(II) complex, [Co(C(8)H(5)O(3))(2)(C(10)H(14)N(2)O)(2)(H(2)O)(2)], the metal centre is located on an inversion center and is coordinated by two 4-formyl-benzoate (FOB), two diethyl-nicotinamide (DENA) ligands and two water mol-ecules in a slightly distorted CoO(4)N(2) octa-hedral geometry. In the crystal structure, O-H⋯O hydrogen bonds link the mol-ecules into infinite chains. π-π contacts between the parallel pyridine rings of neighboring DENA ligands [centroid-centroid distance = 3.652 (3) Å] further stabilize the crystal structure.