Synthesis, spectroscopic properties and biological evaluation of transition metal complexes of salicylhydrazone of anthranilhydrazide: X-ray crystal structure of copper complex

The transition metal complexes of salicylhydrazone of anthranilhydrazide (H2L) were synthesised. The structures of metal complexes were characterized by various spectroscopic [IR, NMR, UV-Vis, EPR], thermal and other physicochemical methods. The single-crystal X-ray diffraction study of [Cu(HL)Cl]center dot H2O reveal its orthorhombic system with space group P2(1)2(1)2 and Z=4. The copper center has a distorted square planar geometry with ONO and Cl as the donor atoms. The ligand and its metal chelates have been screened for their antimicrobial and anti-tubercular activities using serial dilution method. Metal complexes in general have exhibited better antibacterial and antifungal activity than the free ligand and in few cases better than the standard used. Among the bacterial strains used, the complexes are highly potent against Gram-positive strains compared to Gram-negative. Anti-tubercular activity exhibited by the Co(II) complex is comparable with the standard used. (C) 2011 Elsevier B. V. All rights reserved.

Ligational behaviour of (E)-2-amino-N ` -1-(2-hydroxyphenyl) ethylidene]benzohydrazide towards later 3d metal ions: X-ray crystal structure of nickel(IV) complex

Ligational behaviour of (E)-2-amino-N'-1-(2-hydroxyphenyl)ethylidene]benzohydrazide (Aheb) towards later 3d metal ionscopper(II), cobalt(II), manganese(II), zinc(II), cadmium(II) and nickel(IV)] has been studied. Their structures have been elucidated on the basis of spectral (IR, H-1 NMR, UV-Vis, EPR and FAB-mass), elemental analyses, conductance measurements, magnetic moments, and thermal studies. During complexation Ni(II) ion has got oxidized to Ni(IV). The changes in the bond parameters of the ligand on complexation has been discussed by comparing the crystal structure of the ligand with that of its Ni(IV) complex. The X-ray single crystal analysis of Ni(aheb)(2)]Cl-2 center dot 4H(2)O has confirmed an octahedral geometry around the metal ion. EPR spectra of the Cu(II) complex in polycrystalline state at room (300 K) and liquid nitrogen temperature (77 K) were recorded and their salient features are reported. (C) 2014 Elsevier B.V. All rights reserved.

Crystal structure of peanut lectin, a protein with an unusual quaternary structure

The x-ray crystal structure of the tetrameric T-antigen-binding lectin from peanut, M(r) 110,000, has been determined by using the multiple isomorphous replacement method and refined to an R value of 0.218 for 22,155 reflections within the 10- to 2.95-A resolution range. Each subunit has essentially the same characteristic tertiary fold that is found in other legume lectins. The structure, however, exhibits an unusual quaternary arrangement of subunits. Unlike other well-characterized tetrameric proteins with identical subunits, peanut lectin has neither 222 (D2) nor fourfold (C4) symmetry. A noncrystallographic twofold axis relates two halves of the molecule. The two monomers in each half are related by a local twofold axis. The mutual disposition of the axes is such that they do not lead to a closed point group. Furthermore, the structure of peanut lectin demonstrates that differences in subunit arrangement in legume lectins could be due to factors intrinsic to the protein molecule and, contrary to earlier suggestions, are not necessarily caused by interactions involving covalently linked sugar. The structure provides a useful framework for exploring the structural basis and the functional implications of the variability in the subunit arrangement in legume lectins despite all of them having nearly the same subunit structure, and also for investigating the general problem of "open" quaternary assembly in oligomeric proteins.

Crystal structure of Salmonella typhimurium 2-methylcitrate synthase: Insights on domain movement and substrate specificity

2-Methylcitric acid (2-MCA) cycle is one of the well studied pathways for the utilization of propionate as a source of carbon and energy in bacteria such as Salmonella typhimurium and Escherichia coli. 2-Methylcitrate synthase (2-MCS) catalyzes the conversion of oxaloacetate and propionyl-CoA to 2-methylcitrate and CoA in the second step of 2-MCA cycle. Here, we report the X-ray crystal structure of S. typhimurium 2-MCS (StPrpC) at 2.4 A resolution and its functional characterization. StPrpC was found to utilize propionyl-CoA more efficiently than acetyl-CoA or butyryl-CoA. The polypeptide fold and the catalytic residues of StPrpC are conserved in citrate synthases (CSs) suggesting similarities in their functional mechanisms. In the triclinic P1 cell, StPrpC molecules were organized as decamers composed of five identical dimer units. In solution, StPrpC was in a dimeric form at low concentrations and was converted to larger oligomers at higher concentrations. CSs are usually dimeric proteins. In Gram-negative bacteria, a hexameric form, believed to be important for regulation of activity by NADH, is also observed. Structural comparisons with hexameric E. coil CS suggested that the key residues involved in NADH binding are not conserved in StPrpC. Structural comparison with the ligand free and bound states of CSs showed that StPrpC is in a nearly closed conformation despite the absence of bound ligands. It was found that the Tyr197 and Leu324 of StPrpC are structurally equivalent to the ligand binding residues His and Val, respectively, of CSs. These substitutions might determine the specificities for acyl-CoAs of these enzymes. (C) 2010 Elsevier Inc. All rights reserved.

Synthesis, Crystal Structure, and Magnetic Properties of a Ferromagnetically Coupled Angular Trinuclear Copper(11) Complex [Cu3(02CMe)4(bpy)s(HzO)](PF)62

The synthesis, X-ray crystal structure, and magnetic properties of an angular trinuclear copper(II) complex [Cu3(O2CMC)4(bpy)3(H2O)](PF6)2 (1), obtained from a reaction of Cu2(O2CMe)4(H2O)2 With 2,2'-bipyridine (bpy) and NH4PF6 in ethanol, are reported. Complex 1 crystallizes in triclinic space group P1BAR with a = 11.529(1) angstrom, b = 12.121(2) angstrom, c = 17.153(2) angstrom, alpha = 82.01(1)-degrees, beta = 79.42(1)-degrees, gamma = 89.62(1)-degrees, and Z = 2. A total of 6928 data with I > 2.5sigma(I) were refined to R = 0.0441 and R(w) = 0.0557. The structure consists of a trinuclear core bridged by four acetate ligands showing different bonding modes. The coordination geometry at each copper is distorted square-pyramidal with a CuN2O2...O chromophore. The Cu...Cu distances are 3.198(1) angstrom, 4.568(1) angstrom, and 6.277(1) angstrom. There are two monoatomic acetate bridges showing Cu-O-Cu angles of 93.1(1) and 97.5(1)-degrees. Magnetic studies in the temperature range 39-297 K show the presence of a strong ferromagnetically coupled dicopper(II) unit (2J = +158 cm-1) and an essentially isolated copper(II) center (2J' = -0.4 cm-1) in 1. The EPR spectra display an axial spectrum giving g(parallel-to) = 2.28 (A(parallel-to) = 160 X 10(-4) cm-1) and g(perpendicular-to) = 2.06 (A(perpendicular-to) = 12 X 10(-4) cm-1) for the normal copper and two intense isotropic signals with g values 2.70 and 1.74 for the strongly coupled copper pair. The structural features of 1 compare well with the first generation models for ascorbate oxidase.

Novel double insertion of carbon disulfide into two Ru-H bonds of [(dppm)(2)Ru(H)(2)] (dppm = Ph2PCH2PPh2): Synthesis and crystal structure of a methanedithiolate complex

Addition of excess carbon disulfide to cis/trans-[(dPPM)(2)Ru(H)(2)] results in the methanedithiolate complex [(dppm)(2)Ru(eta(2)-S2CH2)] 4 via the intermediacy of cis-[(dppm)(2)Ru(H)(SC(S)H)] 2. The X-ray crystal structure of this species has been determined.

Syntheses and characterization of trans-[NiL2(NCS)2][L = 2-(aminomethyl) pyridine], trans-[NiL02(NSC)2][L0 = 2-(2-aminoethyl)pyridine] and trans-[NiL00 2(NSC)2] [L00 = 2-(2-methylaminoethyl)pyridine] complexes: X-ray single crystal structure of trans-[NiL02(NSC)2] [L0 = 2-(2-aminoethyl)pyridine]

[NiL2(NCS)2] (1) [L = 2-(aminomethyl)pyridine], [NiL02(NCS)2] (2) [(L0) = 2-(2-aminoethyl)pyridine and [NiL00 2(NCS)2] (3) [L00 = 2-(2-methylaminoethyl)pyridine] have been synthesized from solution. All the complexes possess trans geometry as is evident from solid state UV–Vis spectral study and X-ray single crystal structure analysis of complex 2 unambiguously proves trans geometry of the species.

x-ray studies on crystalline complexes involving amino-acids and peptides .10. head-to-tail sequences in the crystal-structure of l-lysine acetate

l-Lysine acetate crystallises in the monoclinic space group P21 with a = 5.411 (1), b = 7.562(1), c= l2.635(2) Å and β = 91.7(1). The crystal structure was solved by direct methods and refined to an R value of 0.049 using the full matrix least squares method. The conformation and the aggregation of lysine molecules in the structure are similar to those found in the crystal structure of l-lysine l-aspartate. A conspicuous similarity between the crystal structures of l-arginine acetate and l-lysine acetate is that in both cases the strongly basic side chain, although having the largest pK value, interacts with the weakly acidic acetate group leaving the α-amino and the α-carboxylate groups to take part in head-to-tail sequences. These structures thus indicate that electrostatic effects are strongly modulated by other factors so as to give rise to head-to-tail sequences which have earlier been shown to be an almost universal feature of amino acid aggregation in the solid state.

X-ray crystal and molecular structure of a hydrated lithium picrate complex of benzo-15-crown-5; An example of non-chelation of the crown

Complexation of alkali and alkaline earth metal ions with crown ethers is well known (1) and chemical and crystallographic studies have been carried out for number of complexes (2,3). The interaction of the metal with the crown ether depends on the nature of the cation and particularly on the basicity of the anion (4) , In this paper we report the crystal and molecular structure of a lithium picrate complex of benzo-15-crown-5, the first x-ray crystallographic study of a lithlum-crown system.

X-ray studies of crystalline complexes involving amino acids. II. The crystal structure of L-arginine L-glutamate

Abstract is not available.

Synthesis, crystal structure and DNA cleavage activity of (aqua)bis(dipyridophenazine)copper(II) complex

A copper(II) complex of dipyridophenazine, viz., [Cu(dppz)(2)(H2O)](ClO4)(2) (I), has been prepared and structurally characterized by X-ray crystallography. The crystal structure of the complex shows a five-coordinate structure in which two N,N-donor dipyridophenazine (dppz) and one aqua ligand bind to the copper(II) center giving Cu-O and Cu-N bond distances in the range of 1.981(6) to 2.043(6) angstrom. The ESI-MS spectrum of 1 in MeCN shows a peak at m/z value of 313 (100%) indicating the dissociation of the aqua ligand in the solution phase. The complex is one-electron paramagnetic (mu(eff), 1.86 mu(B)). It displays a quasi-reversible Cu(II)/Cu(I) redox process at 0.096 V. The complex is an avid binder to CT DNA giving a binding constant value of 3.5 x 10(5) M-1. It shows significant hydrolytic cleavage of supercoiled pUC19 DNA in dark ill the absence of any external agents. The complex exhibits chemical nuclease activity oil treatment with 3-mercaptopropionic acid as a reducing agent forming hydroxyl radicals. Complex 1 is a model synthetic nuclease and hydrolase showing both modes of DNA cleavage under different reaction conditions. The DNA cleavage activity of 1 is significantly better than its phen analogue but similar to that of the bis-dpq complex.

The crystal structure of eulytite Pb3BiV3O12

The crystal structure of Pb3BiV3O12 was solved using single-crystal X-ray diffraction technique. The compound crystallizes in the cubic system View the MathML source (No. 220) with eulytite structure with a = 10.7490(7) Å, V = 1241.95(14) Å3 and Z = 4. The final R1 value of 0.0198 (wR2=0.0384) was achieved for 359 independent reflections during the structure refinement. The Pb2+ and Bi3+ cations occupy the special position (16c) while the oxygen anions occupy the general position (48e) in the crystal structure. Unlike many other eulytite compounds, all the crystallographic positions are fully occupied. The structure consists of edge-shared Pb/Bi octahedra linked at the corners to independent [VO4]3− tetrahedra units, generating a eulytite-type network in the crystal lattice.

beta.-Turn conformation of N-acetyl-L-prolylglycyl-L-phenylalanine. Crystal structure and solution studies

Pro-Gly segments in peptides and proteins are prone to adopt the 0-turn conformation. This paper reports experimental data for the presence of this conformation in a linear tripeptide N-acetyl-L-prolylglycyl-L-phenylalanineb oth in the solid state and in solution. X-ray diffraction data on the tripeptide crystal show that it exists in the type I1 0-turn conformation. CD and proton NMR data show that this conformation persists in trifluoroethanol and methanol solutions in equilibrium with the nonhydrogen-bonded structures. Isomerization around the acetyl-prolyl bond is seen to take place in dimethyl sulfoxide solutions of the tripeptide.