Synthesis and crystal structure of a novel octa-aqua bridged star-shaped Ni4K complex

A penta-nuclear. star-shaped hetero-metallic compound containing a unique Ni4KO8 core has been synthesized. The X-ray single crystal structure analysis reveals that in the complex, [K(Ni(LH)(2))(4)(OH2)(8)](Br)(ClO4)(8)center dot 11H(2)O (LH=(CH3)(2)HN+(CH2)(3)N=CHC6H4O-) the eight coordinate central K+ ion is encapsulated by four terminal [Ni(LH)(2)](2+) units through the double water bridges between K+ and each Ni(II) ions.

The synthesis and properties of [Fe3(CO)11(RCN)] derivatives, and a high-yield general route to mono- and di-substituted derivatives of [Fe3(CO)12]; the crystal and molecular structure of [Fe3(CO)11(NCC6H4-2-Me)]

The clusters [Fe3(CO)11(RCN)] (1: R = Me, C3H5, C6H5, or C6H4-2-Me) have been prepared at low temperature from [Fe3(CO)12] and RCN in the presence of Me3NO. Compounds 1 react essentially quantitatively with a wide range of two-electron donors, L, (viz.: CO, PPh3, P(OMe)3, PPh2H, PPh2Me, PF3, CyNC (Cy = cyclohexyl), P(OEt)3, SbPh3, PBu3, AsPh3, or SnR2 (R = CH(SiMe3)2)) to give [Fe3(CO)11L] (2). In some cases (2), on treatment with Me3NO and then L′ (L′ = a second two-electron donor) yields [Fe3(CO)10LL′] in high yield. The crystal and molecular structures of 1 (L = NCC6H4Me-2) have been determined by a full single crystal structure analysis, and shown to have an axial nitrile coordinated at the unique iron atom, with two CO groups bridging the other two metal atoms.

A simplified, high-yield synthesis, and crystal structure of [tris{bis(2,4,6-triisopropylphenyl)tin}]

The species [{Sn(C2H2iPr3-2,4,6)2}3] has been obtained in a simple, essentially quantitative, synthesis from SnCl2 and ArLi in diethyl ether at low temperature. The crystal structure analysis confirms the trimeric nature of the molecular units but reveals some unusual features. The crystal contains the unusual feature of an asymmetric unit that consists of three units of [{SnAr2}3] in P21/c; the molecular unit is a scalene triangle, showing high consistency between the three molecules, in contrast to analogous trimeric species of silicon or germanium. The SnSn bonds are lengthened (average value 2.942 Å) owing to steric crowding.

Synthesis, crystal structure and hydrolysis of a dinuclear copper(II) complex constructed by N2O donor Schiff base and 4,4 '-bipyridine: discrete supra-molecular ensembles vs. oligomers

The tridentate Schiff base ligand, 7-amino-4-methyl-5-aza-3-hepten-2-one (HAMAH), prepared by the mono-condensation of 1,2diaminoethane and acetylacetone, reacts with Cu(BF4)(2) center dot 6H(2)O to produce initially a dinuclear Cu(II) complex, [{Cu(AMAH)}(2) (mu-4,4'-bipyJ](BF4)(2) (1) which undergoes hydrolysis in the reaction mixture and finally produces a linear polymeric chain compound, [Cu(acac)(2)(mu-4,4'-bipy)](n) (2). The geometry around the copper atom in compound 1 is distorted square planar while that in compound 2 is essentially an elongated octahedron. On the other hand, the ligand HAMAH reacts with Cu(ClO4)(2) center dot 6H(2)O to yield a polymeric zigzag chain, [{Cu(acac)(CH3OH)(mu-4,4'-bipy)}(ClO4)](n) (3). The geometry of the copper atom in 3 is square pyramidal with the two bipyridine molecules in the cis equatorial positions. All three complexes have been characterized by elemental analysis, IR and UV-Vis spectroscopy and single crystal X-ray diffraction studies. A probable explanation for the different size and shape of the reported polynuclear complexes formed by copper(II) and 4,4'-bipyridine has been put forward by taking into account the denticity and crystal field strength of the blocking ligand as well as the Jahn-Teller effect in copper(II). (c) 2007 Elsevier Ltd. All rights reserved.

Anion-pi, Lone-Pair-pi, pi-pi and Hydrogen-Bonding Interactions in a Cu-II Complex of 2-Picolinate and Protonated 4,4 '-Bipyridine: Crystal Structure and Theoretical Studies

A Cu-II complex of protonated 4,4'-bipyridine (Hbyp) and 2-picolinate (pic), [Cu-2(pic)(3)(Hbyp)(H2O)(ClO4)(2)], has been synthesised and characterised by single-crystal X-ray analysis. The structure consists of two copper atoms that have different environments, bridged by a carboxylate group. The equatorial plane is formed by the two bidentate picolinate groups in one Cu-II, and one picolinate, one monodentate 4,4'-bipyridyl ligand and a water molecule in the other. Each copper atom is also weakly bonded to a perchlorate anion in an axial position. One of the coordinated perchlorate groups displays anion-pi interaction with the coordinated pyridine ring. The noncoordinated carboxylate oxygen is involved in lone-pair (l.p.)-pi interaction with the protonated pyridine ring. In addition there are pi-pi and H-bonding interactions in the structure. Bader's theory of "atoms in molecules" (AIM) is used to characterise the anion-pi and l.p.-pi interactions observed in the solid state. A high-level ab initio study (RI-MP2/aug-cc-pVTZ level of theory) has been performed to analyse the anion-pi binding affinity of the pyridine ring when it is coordinated to a transition metal and also when the other pyridine ring of the 4,4'-bipyridine moiety is protonated. Theoretical investigations support the experimental findings of an intricate network of intermolecular interactions, which is characterised in the studied complex, and also indicate that protonation as well as coordination to the transition metal have important roles in influencing the pi-binding properties of the aromatic ring. ((C) Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2009)

First structural analysis of a naphthalene-based poly(ether ketone): Crystal and molecular simulation from X-ray powder data and diffraction modeling

Polycondensation of 2,6-dihydroxynaphthalene with 4,4'-bis(4"-fluorobenzoyl)biphenyl affords a novel, semicrystalline poly(ether ketone) with a melting point of 406 degreesC and glass transition temperature (onset) of 168 degreesC. Molecular modeling and diffraction-simulation studies of this polymer, coupled with data from the single-crystal structure of an oligomer model, have enabled the crystal and molecular structure of the polymer to be determined from X-ray powder data. This structure-the first for any naphthalene-containing poly(ether ketone)-is fully ordered, in monoclinic space group P2(1)/b, with two chains per unit cell. Rietveld refinement against the experimental powder data gave a final agreement factor (R-wp) of 6.7%.

Trichloro-mono-beta-diketonato oxorhenium(V) complexes: synthesis, characterization and crystal structure

Oxorhenium(V) complexes of beta-diketonate systems have been synthesized and isolated in pure form. The red complexes n-Bu4N[ReO(R1COCHCOR2)Cl-3] (acac, R-1=R-2=CH3; bzac, R-1=CH3 and R-2=C6H5; bzbz, R-1=R-2=C6H5) have been characterized by elemental analyses, spectroscopic and other physico-chemical tools. One complex, n-Bu4N[ReO(bzbz)Cl-3] (1c) has been subjected to single-crystal X-ray analysis. In the structure of the anion, the metal has a six-coordinate octahedral environment in which the bidentate -diketone ligand is cis and trans to the terminal oxygen.

Ruthenium (III) complexes of tetradentate NSNO pyridylthioazophenolates: Synthesis, spectral studies, crystal structure and redox properties

A family of ruthenium (III) complexes of tetradentate monobasic NSNO donor chelators (HL) have been synthesized and isolated in their pure form. On chromatographic separation, trans-dichloro and cis-dichloro ruthenium (111) complexes of pyridylthioazophenolates are eluted using 19:1 and 7:3 (v/v) DCM-MeOH mixtures, respectively. Both cis and trans isomers of the dark brown colored ruthenium (111) complexes, having the general formula of [Ru(L)Cl-2], have been characterized by elemental analyses, spectroscopic and other physico-chemical tools. The magnetic moments of both the cis- and trans-[Ru(L)Cl-2] complexes are in the range of 1.71-1.79 BM. One of the complexes, trans-[Ru(L1)Cl-2] (2a), has been subjected to single-crystal X-ray analysis which confirms that the chlorines are in mutually trans positions in the molecule. The EPR spectra of the cis-[Ru(L)Cl-2] complexes (1) in DMF are consistent with the fact that the complexes are low-spin octahedral with one unpaired electron having three different g values (g(x) not equal g(y) not equal g(z)) complexes are monomeric with an octahedral coordination sphere. The electrochemical studies of [Ru(L)Cl,] in DMF show a quasi-reversible voltammogram. The reduction potentials for the cis-isomers are comparatively lower than those of the corresponding trans isomers. On reaction with the bidentate bipyridyl ligand in the presence of AgNO3, the cis-[Ru(L)Cl-2] complexes (1) produce a series of complexes with the general formula [Ru(L)(bpy)(2)](PF6)(2) (3). which have also been characterized by elemental analyses, spectroscopic and other physico-chemical tools. (c) 2006 Elsevier Ltd. All rights reserved.

Zinc(II)-pyridylthioazophenol system: synthesis, characterization and crystal structure

Reactivities of pyridylthioazophenols (1) with zinc(II) salts have been studied and the complexes isolated in pure form and characterized. Pyridylthioazophenols react with zinc( II)acetate in MeOH/EtOH at room temperature to give a series of pyridylsulfinylazophenols (2)but no zinc( II) complex. The sulfoxides (2) have been characterized by IR and NMR. One of the pyridylsulfinylazophenols (2a) has been subjected to single-crystal X-ray analysis in order to confirm details of its structure. A series of dimeric zinc( II) complexes of tetradentate NSNO pyridylthioazophenolates has been isolated through reaction of zinc nitrate in MeOH followed by in situ reaction with azide ion, which acts as a mu-(1,1) bridge. All complexes have been characterized spectroscopically. The detailed structure of one of the dinuclear zinc( II) complexes has been established by a single-crystal X-ray structure determination. In complex 3a two octahedrally coordinated zinc( II) ions are bridged by two end-on azide ions. No reactions of pyridylthioazophenols with zinc chloride in refluxing EtOH have been observed.

Synthesis, crystal structure, magnetic behavior and thermal property of three polynuclear complexes: [M(dca)(2)(H2O)2](n)center dot(hmt)(n) [M = Mn(II), Co(II)] and [Co(dca)(2)(bpds)](n) [dca, dicyanamide; hint, hexamethylenetetramine; bpds, 4,4 '-bipyridyl disulfide]

Three mu(1.5)-dicyanamide bridged Mn(II) and Co(II) complexes having molecular formula [Mn(dca)(2)(H2O)(2)](n)center dot(hmt)(n) (1), [Co(dca)(2) (H2O)(2)](n)center dot(hmt)(n) (2) and [Co(dca)(2)(bpds)](n) (3) [dca = dicyanamide; hmt = hexamethylenetetramine; bpds = 4,4'-bipyridyl disulfide] have been synthesized and characterized by single crystal X-ray diffraction study, low temperature (300-2 K) magnetic measurement and thermal behavior. The X-ray diffraction analysis of 1 and 2 reveals that they are isostructural, comprising of 1D coordination polymers [M(dca)(2)(H2O)(2)](n) [M = Mn(II), Co(II) for 1 and 2. respectively] with uncoordinated hmt molecules located among the chains. The [M(dca)(2)(H2O)(2)](n) chains and the lattice hint molecules are connected through H-bonds resulting in a 3D supramolecular architecture. The octahedral N4O2 chromophore surrounding the metal ion forms via two trans located water oxygens and four nitrogens from four nitrile dca. Complex 3 is a 1D chain formed by two mu(1.5)-dca and one bridging bpds. The octahedral N-6 coordination sphere surrounding the cobalt ions comprises four nitrogens from dca and two from bpds. Low temperature magnetic study indicates small antiferromagnetic coupling for all the complexes. Best fit parameters for 1: J = -0.17 cm(-1), g = -2.03 with R = 6.1 x 10(-4), for 2, J = -0.50 cm(-1), and for 3, J = -0.95 cm(-1). (c) 2005 Elsevier B.V. All rights reserved.

Synthesis and crystal structure characterization of iron(II), cobalt(II) and nickel(II) complexes with 1,3-bis(2-pyridylmethylthio)propane

Three new mononuclear complexes of nitrogen-sulfur donor sets, formulated as (Fe-II(L)Cl-2] (1), [Co-II(L)Cl-2] (2) and [Ni-II(L)Cl-2] (3) where L = 1,3-bis(2-pyridylmethylthio)propane, were synthesized and isolated in their pure form. All the complexes were characterized by physicochemical and spectroscopic methods. The solid state structures of complexes I and 3 have been established by single crystal X-ray crystallography. The structural analysis evidences isomorphous crystals with the metal ion in a distorted octahedral geometry that comprises NSSN ligand donors with trans located pyridine rings and chlorides in cis positions. In dimethylformamide solution, the complexes were found to exhibit Fe-II/Fe-III, co(II)/co(III) and Ni-II/Ni-III quasi-reversible redox couples in cyclic voltammograms with E-1/2 values (versus Ag/AgCl at 298 K) of +0.295, +0.795 and +0.745 V for 1, 2 and 3, respectively. (C) 2009 Elsevier Ltd. All rights reserved.

Synthesis, crystal structure and reactivity of copper(II) complexes of tetradentate N2S2 donor ligands

Two new hexa-coordinated mononuclear copper(II) complexes of two ligands L-1 and L-2 containing NSSN donor sets formulated as [Cu(L)(H2O)(2)](NO3)(2) [1a, L = 1,2-bis(2-pyridylmethylthio)ethane (L-1), 1b L = 1,3-bis(2-pyridyl-methylthio)propane (L-2)] were synthesized and characterized by physico-chemical and spectroscopic methods. In 1a the single crystal X-ray crystallography analysis showed a distorted octahedral geometry about copper(II) ion. The crystal packing evidences pairs of complexes arranged about a center of symmetry and connected through a H-bond occurring between aquo ligands and nitrate anions. On reaction with chloride and pseudohalides (N-3(-) and SCN-), in acetonitrile at ambient temperature. complexes 1 changed to monocationic penta-coordinated mononuclear copper(H) species formulated as [Cu(L)(Cl)]NO3 (2), [Cu(L)(N-3)]NO3 (3). and [Cu(L)(SCN)]NO3 (4). These copper(II) complexes have been isolated in pure form from the reaction mixtures and characterized by physico-chemical and spectroscopic tools. The solid-state structure of 2a, established by X-ray crystallography, shows a trigonal bipyramidal geometry about the metal ion with a trigonality index (tau) of 0.561. (C) 2009 Elsevier B.V. All rights reserved.

Synthesis and crystal structure of [(BU4N)-B-n][Er(pic)(4)] center dot 5.5H(2)O: a new infrared emitter

The new erbium(III) complex of picolinic acid (Hpic), ["Bu4N][Er(pic)(4)].5.5H(2)O, was synthesized and the crystal structure determined by single-crystal X-ray diffraction. The compound was further characterized using IR, Raman, H-1 NMR and elemental analysis. The picolinate ligands (pic(-)) are coordinated through N,O-chelation to the erbium cations, as shown by X-ray diffraction and spectroscopic results, leading to an eight coordinate complex. Photoluminescence measurements were performed for this compound which exhibits infrared emission. (C) 2003 Elsevier B.V. All rights reserved.

Peroxidative bromination and oxygenation of organic compounds: synthesis, X-ray crystal structure and catalytic implications of mononuclear and binuclear oxovanadium(V) complexes containing Schiffbase ligands

Treatment of of (R,R)-N,N-salicylidene cyclohexane 1,2-diamine(H(2)L(1)) in methanol with aqueous NH(4)VO(3) solution in perchloric acid medium affords the mononuclear oxovanadium(V) complex [VOL(1)(MeOH)]-ClO(4) (1) as deep blue solid while the treatment of same solution of (R,R)-N,N-salicylidene cyclohexane 1,2-diamine(H(2)L(1)) with aqueous solution of VOSO(4) leads to the formation of di-(mu-oxo) bridged vanadium(V) complex [VO(2)L(2)](2) (2) as green solid where HL(2) = (R,R)-N-salicylidene cyclohexane 1,2-diamine. The ligand HL(2) is generated in situ by the hydrolysis of one of the imine bonds of HL(1) ligand during the course of formation of complex [VO(2)L(2)](2) (2). Both the compounds have been characterized by single crystal X-ray diffraction as well as spectroscopic methods. Compounds 1 and 2 are to act as catalyst for the catalytic bromide oxidation and C-H bond oxidation in presence of hydrogen peroxide. The representative substrates 2,4-dimethoxy benzoic acid and para-hydroxy benzoic acids are brominated in presence of H(2)O(2) and KBr in acid medium using the above compounds as catalyst. The complexes are also used as catalyst for C-H bond activation of the representative hydrocarbons toluene, ethylbenzene and cyclohexane where hydrogen peroxide acts as terminal oxidant. The yield percentage and turnover number are also quite good for the above catalytic reaction. The oxidized products of hydrocarbons have been characterized by GC Analysis while the brominated products have been characterized by (1)H NMR spectroscopic studies.