Crystal Structure, Theoretical Analysis, and Protein/DNA Binding Activity of Iron(III) Complex Containing Differently Protonated Pyridoxal–S-Methyl-Isothiosemicarbazone Ligands
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ABSTRACT:
SUBMITTER: Jevtovic V
PROVIDER: S-EPMC11241004 | biostudies-literature | 2024 Jun
REPOSITORIES: biostudies-literature
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Project description:The chemistry of several iron(III) porphyrinates containing silanethiolate ligands is described. The complexes are prepared by protonolysis reactions of silanethiols with the iron(III) precursors, [Fe(OMe)(TPP)] and [Fe(OH)(H2O)(TMP)] (TPP = dianion of meso-tetraphenylporphine; TMP = dianion of meso-tetramesitylporphine). Each of the compounds has been fully characterized in solution and the solid state. The stability of the silanethiolate complexes versus other iron(III) porphyrinate complexes containing sulfur-based ligands allows for an examination of their reactivity with several biologically relevant small molecules including H2S, NO, and 1-methylimidazole. Electrochemically, the silanethiolate complexes display a quasi-reversible one-electron oxidation event at potentials higher than that observed for an analogous arenethiolate complex. The behavior of these complexes versus other sulfur-ligated iron(III) porphyrinates is discussed.
| S-EPMC3915880 | biostudies-literature
Project description:Vanadium complexes have gained considerable attention as biologically active compounds. In this contribution, three previously reported dioxovanadium(V) complexes with pyridoxal semicarbazone, thiosemicarbazone, and S-methyl-iso-thiosemicarbazone ligands are theoretically examined. The intermolecular stabilization interactions within crystallographic structures were investigated by Hirshfeld surface analysis. These experimental structures were optimized at the B3LYP-D3BJ/6-311++G(d,p)(H,C,N,O,S)/def2-TZVP(V) level of theory, and crystallographic and optimized bond lengths and angles were compared. High correlation coefficients and low mean absolute errors between these two data sets proved that the selected level of theory was appropriate for the description of the system. The changes in structures and stability were examined by adding explicit solvent molecules. The Quantum Theory of Atoms in Molecules (QTAIM) was employed to analyze the intramolecular interactions with special emphasis on the effect of substituents. A good correlation between electron density/Laplacian and interatomic distance was found. Through molecular docking simulations towards Bovine Serum Albumin (BSA), the binding affinity of complexes was further investigated. The spontaneity of binding in the active position of BSA was shown. Further experimental studies on this class of compounds are advised.
| S-EPMC10976139 | biostudies-literature
Project description:The title compound, poly[(μ2-hydrazine)(μ4-phosphato)iron(III)], [Fe(PO4)(N2H4)] n , was prepared under hydro-thermal conditions. Its asymmetric unit contains one Fe(III) atom located on an inversion centre, one P atom located on a twofold rotation axis, and two O, one N and two H atoms located on general positions. The Fe(III) atom is bound to four O atoms of symmetry-related PO4 tetra-hedra and to two N atoms of two symmetry-related hydrazine ligands, resulting in a slightly distorted FeO4N2 octa-hedron. The crystal structure consists of a three-dimensional hydrazine/iron phoshate framework whereby each PO4 tetra-hedron bridges four Fe(III) atoms and each hydrazine ligand bridges two Fe(III) atoms. The H atoms of the hydrazine ligands are also involved in moderate N-H⋯O hydrogen bonding with phosphate O atoms. The crystal structure is isotypic with the sulfates [Co(SO4)(N2H4)] and [Mn(SO4)(N2H4)].
| S-EPMC4719808 | biostudies-literature
Project description:Structural characterization of the ionic complexes [FeCl2(C26H22P2)2][FeCl4]·0.59CH2Cl2 or [(dppen)2FeCl2][FeCl4]·0.59CH2Cl2 (dppen = cis-1,2-bis-(di-phenyl-phosphane)ethyl-ene, P2C26H22) and [FeCl2(C30H24P2)2][FeCl4]·CH2Cl2 or [(dpbz)2FeCl2][FeCl4]·CH2Cl2 (dpbz = 1,2-bis-(di-phenyl-phosphane)benzene, P2C30H24) demonstrates trans coordination of two bidentate phosphane ligands (bis-phosphanes) to a single iron(III) center, resulting in six-coordinate cationic complexes that are balanced in charge by tetra-chlorido-ferrate(III) monoanions. The trans bis-phosphane coordination is consistent will all previously reported mol-ecular structures of six coordinate iron(III) complex cations with a (PP)2X2 (X = halido) donor set. The complex with dppen crystallizes in the centrosymmetric space group C2/c as a partial-occupancy [0.592 (4)] di-chloro-methane solvate, while the dpbz-ligated complex crystallizes in the triclinic space group P1 as a full di-chloro-methane monosolvate. Furthermore, the crystal studied of [(dpbz)2FeCl2][FeCl4]·CH2Cl2 was an inversion twin, whose component mass ratio refined to 0.76 (3):0.24 (3). Beyond a few very weak C-H⋯Cl and C-H⋯π inter-actions, there are no significant supra-molecular features in either structure.
| S-EPMC6002827 | biostudies-literature
Project description:A theoretical comparative study of a series of five- and six-coordinate iron porphyrins, FeP(L) and FeP(L)(O(2)), has been carried out using DFT methods, where P = porphine and L = imidazole (Im), 1-methylimidazole (1-MeIm), 2-methylimidazole (2-MeIm), 1,2-dimethylimidazole (1,2-Me(2)Im), 4-ethylimidazole (4-EtIm), or histidine (His). Two ligated "picket-fence" iron porphyrins, FeTpivPP(2-MeIm) and FeTpivPP(2-MeIm)(O(2)), were also included in the study for comparison. A number of density functionals were employed in the computations to obtain reliable results. The performance of functionals and basis set effects were investigated in detail on FeP, FeP(Im), and FeP(Im)(O(2)), for which certain experimental information is available and there are some previous calculations in the literature for comparison. Many subtle distinctions in the effects of the different imidazole ligands on the structures and energetics of the deoxy- and oxy iron porphyrins are revealed. While FeP(2-MeIm) is identified to be high spin (S = 2), the ground state of FeP(1-MeIm) may be an admixture of a high-spin (S = 2) and an intermediate-spin (S = 1) state. The ground state of FeP(L)(O(2)) may be different with different L. A weaker Fe-L bond more likely leads to an open-shell singlet ground state for the oxy complex. The 2-methyl group in 2-MeIm, which increases steric contact between the ligand and the porphyrinato skeleton, weakens the Fe-O(2) bond, and thus iron porphyrins with 2-MeIm mimic T-state (low affinity) hemoglobin. The calculated FeP(2-MeIm)-O(2) bonding energy is comparable to the FeTpivPP(2-MeIm)-O(2) one, in agreement with the fact that the picket-fence iron porphyrin binds O(2) with affinity similar to that of myoglobin but different from the result obtained by the CPMD scheme. Im and 4-EtIm closely resemble His, the biologically axial base, and so future computations on hemoprotein models can be simplified safely by using Im.
| S-EPMC2964071 | biostudies-literature
Project description:In the crystal of the title compound, [Fe(NCS)3(H2O)3]·3C6H8N2, the Fe(III) cation is located on a threefold rotation axis and is coordinated by three N atoms of the thiocyanate anions and three water mol-ecules in a fac arrangement, forming a slightly distorted N3O3 octa-hedron. Stabilization within the crystal structure is provided by O-H⋯N hydrogen bonds; the H atoms from coordinating water mol-ecules act as donors to the N atoms of guest 2,3-di-methyl-pyrazine mol-ecules, leading to a three-dimensional supra-molecular framework.
| S-EPMC4438839 | biostudies-literature
Project description:A new iron(iii) complex with 5,7-dichloro-2-methyl-8-quinolinol (HClMQ) as ligands, i.e., [Fe(ClMQ)2Cl] (1), was synthesized and evaluated for its anticancer activity. Compared to the HClMQ ligand, complex 1 showed a higher cytotoxicity towards a series of tumor cell lines, including Hep-G2, BEL-7404, NCI-H460, A549, and T-24, with IC50 values in the range of 5.04-14.35 μM. Notably, the Hep-G2 cell line was the most sensitive to complex 1. Mechanistic studies indicated that complex 1 is a telomerase inhibitor targeting c-myc G-quadruplex DNA and can trigger cell apoptosis via inducing cell cycle arrest and DNA damage.
| S-EPMC6072324 | biostudies-literature
Project description:In bromido-(pyrrolidine-κN)gold(I) bis-(pyrrolidine-κN)gold(I) bromide, [AuBr(pyr)]·[Au(pyr)2]Br (pyr = pyrrolidine, C4H9N), 2, alternating [AuBr(pyr)] mol-ecules and [Au(pyr)2]+ cations are connected by aurophilic contacts to form infinite chains of residues parallel to the b axis. The chains are cross-linked by three N-H⋯Br- hydrogen bonds and an Au⋯Br contact to form a layer structure parallel to the ab plane. Tri-chlorido-(piperidine-κN)gold(III), [AuCl3(pip)] (pip = piperidine, C5H11N), 3, consists of mol-ecules with the expected square-planar coordination at the gold atom, which are connected by an N-H⋯Cl hydrogen bond and an Au⋯Cl contact to form a layer structure parallel to the ac plane. The structures of bis-(piperidinium) tetra-chlorido-aurate(III) chloride, (pipH)2[AuCl4]Cl, 4, and bis-(pyrrolidinium) tetra-bromido-aurate(III) bromide, (pyrH)2[AuBr4]Br, 6, are closely related but not isotypic. Compound 6 crystallizes in space group Ibam; the Au and two Br atoms of the anion lie in the mirror plane x, y, 0, whereas the bromide ions occupy special positions 0, 0.5, 0 and 0, 0.5, 0.25, with site symmetry 2/m. The NH2 group forms a hydrogen bond to one bromide ion, and also a three-centre hydrogen bond to the other bromide atom and to a metal-bonded Br atom. The packing involves chains of hydrogen-bonded pyrrolidinium and bromide ions parallel to the c axis, combined with a layer structure of [AuBr4]- and bromide anions, parallel to the ab plane and involving Au⋯Br and Br⋯Br contacts. Compound 4, however, crystallizes pseudosymmetrically in space group Iba2; two chlorine atoms of the anion lie on the twofold axis 0.5, 0.5, z, and there are two independent cations. The packing is closely similar to that of 6, but there are no N-H⋯Cl hydrogen bonds to metal-bonded chlorines. The contact distances Au⋯Cl are appreciably longer than their Au⋯Br counterparts in 6, whereas the Cl⋯Cl contact is much shorter than Br⋯Br in 6. Tri-bromido-(piperidine-κN)gold(III) crystallizes as its di-chloro-methane solvate, [AuBr3(pip)]·CH2Cl2, 7. It too displays a square-planar coordination at the gold atom. The packing involves hydrogen bonds N-H⋯Br, stacking of neighbouring AuBr3 units by Au⋯Br contacts, and a short Br⋯Br contact; these combine to form a layer structure parallel to the ac plane.
| S-EPMC10626954 | biostudies-literature
Project description:Since the discovery of perchlorate salts on Mars and the known occurrence of ferric salts in the regolith, there is a distinct possibility that the title compound could form on the surface of Mars. [Fe(H2O)6](ClO4)3·3H2O was crystallized from aqueous solutions at low temperatures according to the solid-liquid phase diagram. It consists of Fe(H2O)6 octa-hedra (point group symmetry -3.) and perchlorate anions (point group symmetry .2) as well as non-coordinating water mol-ecules, as part of a second hydrogen-bonded coordination sphere around the cation. The perchlorate appears to be slightly disordered, with major-minor component occupancies of 0.773 (9):0.227 (9).
| S-EPMC4257414 | biostudies-literature
Project description:Two ytterbium(III) complexes comprising alkynylamidinate ligands, namely bis-(η5-cyclo-penta-dien-yl)(3-cyclo-propyl-N,N'-diiso-propyl-propynamidinato-κ2N,N')ytterbium(III), [Yb(C5H5)2(C12H19N2)] or Cp2Yb[( i Pr2N)2C-C≡C-c-C3H5] (1) and tris-(3-phenyl-N,N'-di-cyclo-hexyl-propynamidinato-κ2N,N')ytterbium(III), [Yb(C21H27N2)3] or Yb[(CyN)2C-C≡C-Ph]3 (Cy = cyclo-hex-yl) (2) have been synthesized and structurally characterized. Both complexes are monomers; for complex 2, the contribution to the scattering from highly disordered toluene solvent molecules in these voids was removed with the SQUEEZE routine [Spek (2015). Acta Cryst. C71, 9-18] in PLATON. The stated crystal data for Mr, μ etc. do not take these into account.
| S-EPMC5120694 | biostudies-literature