Novel Products of Nitrosation of a Series of Trihydroxybenzene Derivatives and Their Complexation with Cu(II), Cd(II) and Fe(III): Synthesis, Characterization, and Theoretical Modeling

Abstract

Three novel bis-and trinitroso compounds derived from 1,3,5trihydrohybenzene (phloroglucinol), 2,4,6-trihydroxy benzoic acid, and 2,4,6-trihydroxyacetophenone were isolated, their spectral characteristics, ionization constants and thermodynamic parameters of dissociation process were calculated. The comparison of the stability of nitroso and hydroxylimino tautomeric forms was performed by DFT calculations. Nine complexes of the ligands with Cu(II), Cd(II), and Fe(III), were isolated and studied by elemental analyses, X Ray analysis and spectroscopic methods. According to the crystal structure determination, the Cd complex with the phloroglucinol based ligand exists in the form of a binuclear compound. The QTAIM Bader topological analysis indicated that the binuclearity of the Cd complex is due to strong interatomic interactions between Cd atoms with bifurcate carbonyl groups of the ligands and strong H-interactions involving coordinated and lattice water molecules. The equilibria of reactions of complex formation of the organic species with Cu 2 + , Cd 2 + , and Fe 3 + was studied by spectrophotometric titration, and the composition of the complexes in solutions and their stability constants were calculated. The ability of the isolated organics to remove metal cations from the aqueous solutions was studied in the pH interval 3-6 and the rate of Cu 2 + removal from aqueous solutions was found close to 100 %.

Crystallographic and computational characterization and in silico target fishing of six aromatic and aliphatic sulfonamide derivatives

“…In the crystal of compound I (containing no substituents in the former benzenesulfonyl chloride fragment of the molecule) centrosymmetric dimeric associates are realized with the participation of sulfonamide fragments, in which the molecules are connected by intermolecular hydrogen bonds of the N-H…O type (figure 5) with the parameters: H…O = 2.309 Å, N…O = 3.546 Å, NHO = 119.8°. This differs from previously reported structures of relevant sulfonamides [9][10][11][12][13][14][15][16][17][18] in which the lattice stabilization occurs by the formation of monomeric structures with linear systems of intermolecular N-H…O bonding. The exception is p-amino substituted sulfonamides in which the lattices are stabilized by a branched architecture of hydrogen bonds involving amino groups and sulfonamide fragments of neighbouring molecules [13,14,17,18].…”

“…Some bond lengths and bond angles of sulfonamide fragments are presented in tables 2 and 3. As can be seen, their main characteristics differ little from each other and from the values known in the literature [7][8][9][10][11][12][13][14][15][16][17][18][19].…”

Crystallographic and computational characterization and in silico target fishing of six aromatic and aliphatic sulfonamide derivatives

“…In the crystal of compound I (containing no substituents in the former benzenesulfonyl chloride fragment of the molecule) centrosymmetric dimeric associates are realized with the participation of sulfonamide fragments, in which the molecules are connected by intermolecular hydrogen bonds of the N-H…O type (figure 5) with the parameters: H…O = 2.309 Å, N…O = 3.546 Å, NHO = 119.8°. This differs from previously reported structures of relevant sulfonamides [9][10][11][12][13][14][15][16][17][18] in which the lattice stabilization occurs by the formation of monomeric structures with linear systems of intermolecular N-H…O bonding. The exception is p-amino substituted sulfonamides in which the lattices are stabilized by a branched architecture of hydrogen bonds involving amino groups and sulfonamide fragments of neighbouring molecules [13,14,17,18].…”

“…Some bond lengths and bond angles of sulfonamide fragments are presented in tables 2 and 3. As can be seen, their main characteristics differ little from each other and from the values known in the literature [7][8][9][10][11][12][13][14][15][16][17][18][19].…”

Novel Azo Compounds Derived from Thiazolidine-4-one: Synthesis, Metal Complexation, Coloristic Properties, and Biological Activity

“…In the IR spectra of the synthesized substances, several regions of characteristic vibrations are observed, among which absorption in the region of 2180–2200 cm –1 (νCN) and 1720–1695 cm –1 (νCO) can be assigned ( Table , Supporting Information ). − …”

Synthesis, characterization, and sorption activity of novel azo-colorants derived from phloroglucinol and antipyrine and their metal complexes

“…In previous work, 33 some derived phloroglucinols were successfully nitrosated using HCl and NaNO 2 to archive the nitroso compound, which exists as tautomeric oximes. These chelating oxime ligands could be used as eco-friendly sorbents for removing heavy metal cations from the environment.…”

“… 31,32 A series of bis- and trinitroso compounds derived from 1,3,5-trihydroxybenzene (phloroglucinol), 2,4,6-trihydroxy benzoic acid, and 2,4,6-trihydroxyacetophenone, their tautomeric and ionic equilibria as well as complex formation with transitional metal cations was reported. 33 The results showed that the isolated organics could be used as potential ligands for removing metal cations from aqueous solutions in the pH interval 3–5.…”

Crystallographic and computational characterization and in silico target fishing of six aromatic and aliphatic sulfonamide derivatives

“…In the crystal of compound I (containing no substituents in the former benzenesulfonyl chloride fragment of the molecule) centrosymmetric dimeric associates are realized with the participation of sulfonamide fragments, in which the molecules are connected by intermolecular hydrogen bonds of the N-H…O type (figure 5) with the parameters: H…O = 2.309 Å, N…O = 3.546 Å, NHO = 119.8°. This differs from previously reported structures of relevant sulfonamides [9][10][11][12][13][14][15][16][17][18] in which the lattice stabilization occurs by the formation of monomeric structures with linear systems of intermolecular N-H…O bonding. The exception is p-amino substituted sulfonamides in which the lattices are stabilized by a branched architecture of hydrogen bonds involving amino groups and sulfonamide fragments of neighbouring molecules [13,14,17,18].…”

“…Some bond lengths and bond angles of sulfonamide fragments are presented in tables 2 and 3. As can be seen, their main characteristics differ little from each other and from the values known in the literature [7][8][9][10][11][12][13][14][15][16][17][18][19].…”

Novel Azo Compounds Derived from Thiazolidine-4-one: Synthesis, Metal Complexation, Coloristic Properties, and Biological Activity

“…In the IR spectra of the synthesized substances, several regions of characteristic vibrations are observed, among which absorption in the region of 2180–2200 cm –1 (νCN) and 1720–1695 cm –1 (νCO) can be assigned ( Table , Supporting Information ). − …”

Synthesis, characterization, and sorption activity of novel azo-colorants derived from phloroglucinol and antipyrine and their metal complexes

“…In previous work, 33 some derived phloroglucinols were successfully nitrosated using HCl and NaNO 2 to archive the nitroso compound, which exists as tautomeric oximes. These chelating oxime ligands could be used as eco-friendly sorbents for removing heavy metal cations from the environment.…”

“… 31,32 A series of bis- and trinitroso compounds derived from 1,3,5-trihydroxybenzene (phloroglucinol), 2,4,6-trihydroxy benzoic acid, and 2,4,6-trihydroxyacetophenone, their tautomeric and ionic equilibria as well as complex formation with transitional metal cations was reported. 33 The results showed that the isolated organics could be used as potential ligands for removing metal cations from aqueous solutions in the pH interval 3–5.…”

Crystallographic and computational characterization and in silico target fishing of six aromatic and aliphatic sulfonamide derivatives

“…In the crystal of compound I (containing no substituents in the former benzenesulfonyl chloride fragment of the molecule) centrosymmetric dimeric associates are realized with the participation of sulfonamide fragments, in which the molecules are connected by intermolecular hydrogen bonds of the N-H…O type (figure 5) with the parameters: H…O = 2.309 Å, N…O = 3.546 Å, NHO = 119.8°. This differs from previously reported structures of relevant sulfonamides [9][10][11][12][13][14][15][16][17][18] in which the lattice stabilization occurs by the formation of monomeric structures with linear systems of intermolecular N-H…O bonding. The exception is p-amino substituted sulfonamides in which the lattices are stabilized by a branched architecture of hydrogen bonds involving amino groups and sulfonamide fragments of neighbouring molecules [13,14,17,18].…”

“…Some bond lengths and bond angles of sulfonamide fragments are presented in tables 2 and 3. As can be seen, their main characteristics differ little from each other and from the values known in the literature [7][8][9][10][11][12][13][14][15][16][17][18][19].…”

Novel Azo Compounds Derived from Thiazolidine-4-one: Synthesis, Metal Complexation, Coloristic Properties, and Biological Activity

“…In the IR spectra of the synthesized substances, several regions of characteristic vibrations are observed, among which absorption in the region of 2180–2200 cm –1 (νCN) and 1720–1695 cm –1 (νCO) can be assigned ( Table , Supporting Information ). − …”

Synthesis, characterization, and sorption activity of novel azo-colorants derived from phloroglucinol and antipyrine and their metal complexes

“…In previous work, 33 some derived phloroglucinols were successfully nitrosated using HCl and NaNO 2 to archive the nitroso compound, which exists as tautomeric oximes. These chelating oxime ligands could be used as eco-friendly sorbents for removing heavy metal cations from the environment.…”

“… 31,32 A series of bis- and trinitroso compounds derived from 1,3,5-trihydroxybenzene (phloroglucinol), 2,4,6-trihydroxy benzoic acid, and 2,4,6-trihydroxyacetophenone, their tautomeric and ionic equilibria as well as complex formation with transitional metal cations was reported. 33 The results showed that the isolated organics could be used as potential ligands for removing metal cations from aqueous solutions in the pH interval 3–5.…”