Yasemin Süzen

Phosphorus–nitrogen compounds part 27. Syntheses, structural characterizations, antimicrobial and cytotoxic activities, and DNA interactions of new phosphazenes bearing secondary amino and pendant (4-fluorobenzyl)spiro groups

A number of partly (7-9) and fully (10a-12d, Scheme 1) substituted mono(4-fluorobenzyl)spiro cyclotriphosphazenes was prepared. The structures of the compounds were determined by MS, FTIR, 1D and 2D NMR techniques. The crystal structures of 9, 11b and 12b were verified by X-ray diffraction analysis. In vitro cytotoxic activity of the phosphazenes (10a-12d) against HeLa cervical cancer cell lines was evaluated. Compound 12c was found to be the most effective, as it is a cytotoxic reagent that might activate apoptosis by altering mitochondrial membrane potential. Compounds 10b, 11b and 12b showed very good activity against yeast strains Candida tropicalis and Candida albicans. BamHI and HindIII digestion results demonstrate that the compounds (10a-12a, 10b-12b, 10d-12d), and (9, 10c-12c) bind with G/G and A/A nucleotides, respectively.

Phosphorus-Nitrogen Compounds: Part 25. Syntheses, Spectroscopic, Structural and Electrochemical Investigations, Antimicrobial Activities, and DNA Interactions of Ferrocenyldiaminocyclotriphosphazenes

Abstract The condensation reactions of hexachlorocyclotriphosphazene (N3P3Cl6) with mono (1 and 2) and bisferrocenyldiamines (3–5 and 7) resulted in the formation of tetrachloro mono- (8 and 9) and bisferrocenylspirocyclotriphosphazenes (10–13). In addition the tetramorpholino mono- (8a and 9a) and bisferrocenylphosphazenes (10a–12a) were obtained from the reactions of the corresponding tetrachlorophosphazenes (8–12) with excess morpholine. The structures of all the phosphazenes were determined using FTIR, MS, 1H, 13C, and 31P NMR and 2-dimensional NMR techniques. The structures of 9a and 13 were determined by single crystal X-ray diffraction techniques. Cyclic voltammetric investigations of compounds 8a, 9a, and 11a revealed that ferrocene redox centers undergo reversible oxidation. These ferrocenylphosphazenes appear to be quite robust electrochemically. Interactions between the compounds 8a, 9a, 11a, and 12a and pBR322 plasmid DNA were investigated by agarose gel electrophoresis. [Supplementary materials are available for this article. Go to the publishers online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional text and figures.] GRAPHICAL ABSTRACT

Two dimensional cyano-bridged heteropolynuclear complex containing Pd ···π interactions

Abstract The heteronuclear complex, [Cd(NH3)2(μ-ampy)Pd(μ-CN)2(CN)2]n (1) (ampy = 4-aminomethylpyridine), was synthesized and characterized by vibrational (FT-IR and Raman) spectroscopy, elemental and thermal analyses and single crystal X-ray diffraction techniques. The complex crystallizes in the triclinic system, space group P-1. The Cd(II) ion exhibits a distorted octahedral coordination by two different N-atoms from two symmetrically equivalent ampy ligands, two ammine ligands and two bridging cyano groups, whereas the Pd(II) ion has square planar coordination and is coordinated by four cyano ligands. The tetracyanopalladate(II) anion is coordinated to the adjacent two Cd(II) ions to generate a one-dimensional chain. The adjacent 1D chains are connected by the μ-ampy bridging ligands to form a 2D network. The 2D layers are further linked by Pd···π and hydrogen bonding interactions to generate a 3D supramolecular network. The decomposition reaction takes places in the temperature range of 40–900 °C in the static air atmosphere.

Synthesis and characterization of some metal complexes of a proton transfer salt, and their inhibition studies on carbonic anhydrase isozymes and the evaluation of the results by statistical analysis

Abstract A novel proton transfer compound (HMeOABT) + (HDPC)− (1) and its Fe(III), Co(II), Ni(II) and Cu(II) complexes (2–5) have been prepared and characterized by spectroscopic techniques. Complex 4 has distorted octahedral conformation revealed by single crystal X-ray diffraction method. Structures of the other complexes might be proposed as octahedral according to experimental data. All compounds were also evaluated for their in vitro inhibition effects on hCA I and II for their hydratase and esterase activities. Although there is no inhibition for hydratase activities, all compounds have inhibited the esterase activities of hCA I and II. Data have been analyzed by using a one-way analysis of variance. The comparison of the inhibition studies of 1–5 to parent compounds indicates that 1–5 have superior inhibitory effects. The inhibition effects of 2–5 are also compared to inhibitory properties of the metal complexes of MeOABT and H2DPC, revealing an improved transfection profile.

Di-μ-nicotinamide-κ2O:N1;κ2N1:O-bis­[aqua­bis­(4-meth­oxy­benzoato-κO)copper(II)]

The asymmetric unit of the centrosymmetric dinuclear title compound, [Cu2(C8H7O3)4(C6H6N2O)2(H2O)2], contains one half of the complex molecule. Each CuII atom is five-coordinated by one N atom from one bridging nicotinamide ligand and one O atom from another symmetry-related bridging nicotinamide ligand, two O atoms from two 4-methoxybenzoate ligands, and one water molecule, forming a distorted square-pyramidal geometry. Intermolecular O—H⋯O and N—H⋯O hydrogen bonds link the molecules into layers parallel to (01). π–π interactions, indicated by short intermolecular distances of 3.801 (1) Å between the centroids of the benzene rings and 3.653 (1) Å between the centroids of the pyridine rings, further stabilize the structure.

Bis[μ-4-(dimethyl­amino)­benzoato]-κ3O,O′:O;κ3O:O,O′-bis­{aqua­[4-(dimethyl­amino)­benzoato-κ2O,O′](nicotinamide-κN1)cadmium(II)}

In the centrosymmetric dimeric CdII title compound, [Cd2(C9H10NO2)4(C6H6N2O)2(H2O)2], each seven-coordinated CdII atom is chelated by the carboxylate groups of the two 4-(dimethylamino)benzoate (DMAB) anions; the two monomeric units are bridged through the two O atoms of the two carboxyl groups. In the crystal structure, intermolecular O—H⋯O, N—H⋯O and C—H⋯O hydrogen bonds link the molecules into a three-dimensional network. π–π contacts between the pyridine rings [centroid–centroid distance = 3.974 (1) Å] may further stabilize the structure. Weak C—H⋯π interactions are also observed.

Diaqua­(isonicotinamide-κN1)(4-meth­oxy­benzoato-κ2O,O′)(4-meth­oxy­benzoato-κO)cobalt(II)

In the title complex, [Co(C8H7O3)2(C6H6N2O)(H2O)2], the CoII atom is coordinated by three O atoms from two 4-methoxybenzoate ligands, which act in different modes, viz. monodentate and bidentate, two water molecules and one N atom of the isonicotinamide ligand in a distorted octahedral geometry. The monodentate-coordinated carboxylate group is involved in an intramolecular O—H⋯O hydrogen bond with the coordinated water molecule. In the crystal structure, intermolecular O—H⋯O and N—H⋯O hydrogen bonds link the molecules into layers parallel to the ab plane. The crystal packing is further stabilized by weak C—H⋯O hydrogen bonds and π–π interactions indicated by the short distance of 3.6181 (8) Å between the centroids of the benzene and pyridine rings of neighbouring molecules.

Aqua­bis(isonicotinamide-κN 1)bis­(4-methyl­benzoato)-κO;κ2 O,O′-cadmium(II) monohydrate

In the crystal structure of the title compound, [Cd(C8H7O2)2(C6H6N2O)2(H2O)]·H2O, the CdII cation is coordinated by two 4-methylbenzoate (PMB) anions, two isonicotinamide (INA) ligands and one water molecule in a distorted octahedral CdN2O4 geometry. One of PMB ions acts as a bidentate ligand while the other and the two INA are monodentate ligands. An O—H⋯O hydrogen bond links the uncoordinated water molecule to the carboxyl groups of the complex. The dihedral angles between the carboxyl groups and the adjacent benzene rings are 10.28 (11) and 21.24 (9)°, while the two benzene rings and the two pyridine rings are oriented at dihedral angles of 6.90 (4) and 88.64 (4)°, respectively. In the crystal structure, O—H⋯O and N—H⋯O hydrogen bonds link the molecules into a supramolecular structure. A π–π contact between the benzene rings [centroid–centroid distance = 3.911 (1) Å] may further stabilize the crystal structure. Weak C—H⋯π interactions involving the pyridine rings also occur in the crystal structure.

Diaqua-bis-(N,N-diethyl-nicotinamide-κN)bis[4-(dimethyl-amino)-benzoato-κO]cobalt(II).

The centrosymmetric title NiII complex, [Ni(C9H10NO2)2(C10H14N2O)2(H2O)2], contains two dimethylaminobenzoate (DMAB), two diethylnicotinamide (DENA) ligands and two water molecules, all of them monodentate. The four O atoms in the equatorial plane around the NiII atom form a slightly distorted square-planar arrangement, while the slightly distorted octahedral coordination is completed by the two pyridine N atoms of the DENA ligands in axial positions. The NiII atom is displaced by 0.681 (1) Å out of the least-squares plane of the carboxylate group. The dihedral angle between the carboxylate group and the adjacent benzene ring is 5.61 (7)°, while the pyridine and benzene rings are oriented at a dihedral angle of 73.20 (4)°. An intramolecular O—H⋯O hydrogen bond results in the formation of a six-membered ring with a twisted conformation. In the crystal structure, intermolecular O—H⋯O and C—H⋯O hydrogen bonds link molecules into a three-dimensional network. Two weak C—H⋯π interactions are also present.

4',4',6',6'-Tetrachloro-3,4-dihydro-3-(6-methylpyridin-2-yl)spiro[1,3,2-benzoxazaphosphinine-2,2'-(2lambda5,4lambda5,6lambda5-cyclotriphosphazene)].

The title compound, C13H12Cl4N5OP3, is a phosphazene derivative with a bulky substituted spirocyclic ring. The C3NPO spirocyclic ring has a twist-boat conformation, while the phosphazene ring has a very flattened boat conformation.