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1.
The heterovalent trinuclear cobalt complexes [Co2IIIL4 i · CoII(H2O)4] · nXmY (L i are deprotonated Schiff bases derived from substituted salicylaldehydes and β-alanine; i = 1–3) were obtained and characterized. An X-ray diffraction study of the trinuclear cobalt complex with N-(2-carboxyethyl)salicylaldimine showed that the central Co(II) ion and the terminal Co(III) ions are linked by bridging carboxylate groups. Either terminal Co(III) atom is coordinated to two ligand molecules. They form an octahedral environment consisting of two azomethine N atoms, two phenolate O atoms, and two O atoms of two carboxylate groups. The central Co(II) atom is coordinated to four water molecules and to two O atoms of two bridging carboxylate ligands involved in the coordination sphere of the terminal Co(III) atoms.  相似文献   

2.
The structure of compound I: poly-diaqua(μ-imidazole-4,5-dicarboxylato-N,O; -O′; -O′′, -O′′′) calcium(II) monohydrate [Ca(C5H2N2O4)(H2O)2·H2O] is built of molecular sheets in which imidazole-4,5-dicarboxylate ligands bridge the metal ions using both carboxylate groups, each bidentate. Ca(II) is coordinated by six oxygen atoms and one hetero-ring nitrogen atom distributed at the apices of a capped tetragonal bipyramid. The basal plane of the pyramid is formed by two carboxylate oxygen atoms [d(Ca–O2?=?2.374(1)?Å, d(Ca–O4)?=?2.412(1)?Å] and two water oxygen atoms [d(Ca–O5)?=?2.384(1)?Å, d(Ca–O6)?=?2.455(1)?Å], the capped position is occupied by the carboxylate oxygen atom O3 [d(Ca–O3)?=?2.325(1)?Å], the hetero-ring nitrogen atom [d(Ca–N2)?=?2.523(1)?Å] and the carboxylate oxygen atom O4 [d(Ca–O2)?= 2.412(1)?Å] form the apices of the prism. The solvation water molecule plays a significant role in a framework of hydrogen bonds responsible for the stability of the crystal. The structure of compound II: trans-tetraquadi(H-imidazole-4,5-dicarboxylato-N,O) calcium(II) monohydrate, [Ca(C5H3N2O4)2(H2O)4·H2O] consists of monomers in which the Ca(II) ion is located on a centre of symmetry. The coordination around the Ca(II) is a strongly deformed pentagonal bipyramidal with the imidazole-4,5-dicarboxylate (4,5-IDA) ligands in the trans arrangement forming a dihedral angle of 68.3°. An imidazole-ring nitrogen atom [d(Ca–N)?=?2.632(2)?Å] and one carboxylate O atom [d(Ca–O)?=?2.531(2)?Å] from each ligand coordinate to the metal ion. The coordination is completed by four water oxygen atoms [d(Ca–O)?=?2.393(2)?Å] and [d(Ca–O)?=?2.367(2)?Å]. The coordinated water molecules act as hydrogen bond donors and acceptors to the unbonded carboxylate oxygen atoms in adjacent monomers giving rise to a three-dimensional molecular network.  相似文献   

3.
Transition metal complexes of arginine (using Co(II), Ni(II), Cu(II) and Zn(II) cations separately) were synthesized and characterized by FTIR, TG/DTA‐DrTG, UV‐Vis spectroscopy and elemental analysis methods. Cu(II)‐Arg complex crystals was found suitable for x‐ray diffraction studies. It was contained, one mole CuII and Na+ ions, two arginate ligands, one coordinated aqua ligand and one solvent NO3? group in the asymmetric unit. The principle coordination sites of metal atom have been occupied by two N atoms of arginate ligands, two carboxylate O atoms, while the apical site was occupied by one O atom for CuII cation and two O atoms for CoII, NiII, ZnII atoms of aqua ligands. Although CuII ion adopts a square pyramidal geometry of the structure. CoII, NiII, ZnII cations have octahedral due to coordination number of these metals. Neighbouring chains were linked together to form a three‐dimensional network via hydrogen‐bonding between coordinated water molecule, amino atoms and O atoms of the bridging carboxylate groups. CuII complex was crystallized in the monoclinic space group P21, a = 8.4407(5) Å, b = 12.0976(5) Å, c = 10.2448(6) Å, V = 1041.03(10) Å3, Z = 2. Structures of the other metal complexes were similar to CuII complex, because of their spectroscopic studies have in agreement with each other. Copper complex has shown DNA like helix chain structure. Lastly, anti‐bacterial, anti‐microbial and anti‐fungal biological activities of complexes were investigated.  相似文献   

4.
The aquaorotatotriethanolaminenickel(II) monohydrate, [Ni(HOr)(H2O)(tea)]·H2O ( 1 ), was synthesized and characterized by means of elementel analysis, IR and UV‐Vis, spectroscopy, magnetic susceptibility, thermal analysis and X‐ray diffraction techniques. The nickel ion in [Ni(C5H2N2O4)(H2O)(N(C2H4OH)3)] is chelated to the deprotonated N3 pyrimidine atom and to the carboxylate oxygen atom of the bidentate orotate dianion, and to the one nitrogen and two oxygen atoms of the tridentate triethanolamine molecule and its octahedral geometry is completed by an aqua ligand. It crystallizes in the monoclinic system, space group P21/c with lattice parameters a = 7.1528(5) Å, b = 19.4903(14) Å, c = 11.8085(8) Å, β = 106.237(5)°, V = 1580.55(19) Å3, Z = 4. An extensive three dimensional network of Ow‐H…O, N‐H…O and O‐H…O hydrogen bonds, π‐π and π‐ring interactions are responsible for crystal stabilization. The decomposition reaction take places in the temperature range 20‐1000 °C in the static air atmosphere. Thermal decomposition of 1 proceeds in three stages.  相似文献   

5.
The coordination compounds [CoL2Cl2] (I) and [CdL2(H2O)2(NO3)2] (II) have been synthesized by the reaction of CoCl2 · 6H2O and Cd(NO3)2 · 4H2O with L = 2-amino-4-methylpyrimidine (Ampym, C5H7N3), and their structures have been solved. The crystals of complex I are triclinic, space group $P\bar 1$ , a = 5.627(1) Å, b = 11.191(1) Å, c = 12.445(1) Å, α = 81.00(1)°, β = 77.21(1)°, γ = 76.18(1)°, V = 737.7(2) Å3, ρcalcd = 1.567 g/cm3, Z = 2. The crystals of complex II are monoclinic, space group P21/c, a = 10.390(1) Å, b = 11.982(1) Å, c = 7.624(1) Å, β = 102.61(1)°, V = 926.1(2) Å3, ρcalcd = 1.760 g/cm3, Z = 2. Discrete [CoL2Cl2] moieties are realized in the structure of complex I. The cobalt atom is tetrahedrally coordinated to the two nitrogen atoms of crystallographically nonequivalent ligands L and two chlorine atoms (Co(1)-Navg, 2.051(4)Å; Co(1)-Cl(1), 2.241(1) Å; Co(1)-Cl(2), 2.263 Å; bond angles at the cobalt atom lie within a range of 102.1°–118.6°). The complexes are linked into supramolecular zigzag chains by N-H...N(Cl) hydrogen bonds. In the structure of complex II, the Cd2+ ion (at the inversion center) is coordinated in pairs to the nitrogen atoms of ligand L and the O(NO3) and O(H2O) oxygen atoms. The coordination of the Cd2+ ion is distorted octahedral (Cd(1)-N(1), 2.341Å; Cd(1)-O(1), 2.340(4) Å; Cd(1)-O(4), 2.327(3) Å; bond angles at the cadmium atom lie within a range of 79.1°–100.9°). N-H...N hydrogen bonds link the complexes into supramolecular chains. These chains are linked into a supramolecular framework by the O-H...O hydrogen bonds between water molecules and NO3 groups.  相似文献   

6.
This paper presents a facile and rapid synthesis route of metallic Ni and Co nanocrystallites at ~150 °C in the mixture composed of the corresponding metal nitrates and 1,3-propanediol, as reducing agent. The metal oxides NiO, CoO, Co3O4 nanocrystallites were, also, successfully synthesized by thermal decomposition at 300 °C of the hydroxycarboxylate coordination products, obtained in the redox reaction between 1,3-propanediol and Ni(II) and Co(II) nitrates. The formation of the Ni(II) and Co(II) hydroxycarboxylate complexes depends on the diol which generates the carboxylate anion, the transition metal and the process parameters. Ni(II) and Co(II) nanocomposites were also synthesized by thermal decomposition of the complex combinations formed within the pores of the hybrid silica gels. One of the purposes of the present study was to investigate the phase constitution of the composites obtained in similar synthesis conditions, from Ni(II) and Co(II) complex combinations embedded in silica gels. These gels were submitted to various thermal treatments and the changes occurring during these treatments were described by X-ray diffraction. Thermal analysis is an excellent tool for the study of the processes implied in the formation and decomposition of the Co(II) and Ni(II) carboxylate complexes. X-ray diffraction evidenced the nanometer sized metal and/or metal oxide phases.  相似文献   

7.
The title compounds, hexa­aqua­cobalt(II) bis­(hypophosphite), [Co(H2O)6](H2­PO2)2, and hexa­aqua­cobalt(II)/nickel(II) bis(hypophosphite), [Co0.5Ni0.5(H2O)6](H2PO2)2, are shown to adopt the same structure as hexa­aqua­magnesium(II) bis­(hypophosphite). The packing of the Co(Ni) and P atoms is the same as in the structure of CaF2. The CoII(NiII) atoms have a pseudo‐face‐centred cubic cell, with a = b~ 10.3 Å, and the P atoms occupy the tetrahedral cavities. The central metal cation has a slightly distorted octahedral coordination sphere. The geometry of the hypophosphite anion in the structure is very close to ideal, with point symmetry mm2. Each O atom of the hypophosphite anion is hydrogen bonded to three water mol­ecules from different cation complexes, and each H atom of the hypophosphite anion is surrounded by three water mol­ecules from further different cation complexes.  相似文献   

8.
trans‐Di­aqua­bis­(iso­quinoline‐1‐carboxyl­ato‐κ2N,O)­cobalt(II) dihydrate, [Co(C10H6NO2)2(H2O)2]·2H2O, and trans‐di­aqua­bis­(iso­quinoline‐1‐carboxyl­ato‐κ2N,O)­nickel(II) dihydrate, [Ni(C10H6NO2)2(H2O)2]·2H2O, contain the same isoquinoline ligand, with both metal atoms residing on a centre of symmetry and having the same distorted octahedral coordination. In the former complex, the Co—O(water) bond length in the axial direction is 2.167 (2) Å, which is longer than the Co—O(carboxylate) and Co—N bond lengths in the equatorial plane [2.055 (2) and 2.096 (2) Å, respectively]. In the latter complex, the corresponding bond lengths for Ni—O(water), Ni—O(carboxylate) and Ni—N are 2.127 (2), 2.036 (2) and 2.039 (3) Å, respectively. Both crystals are stabilized by similar stacking interactions of the ligand, and also by hydrogen bonds between the hydrate and coordinated water molecules.  相似文献   

9.
The title compound, [Co(C7H6NO2)2(H2O)4]·4H2O, contains a CoII ion lying on a crystallographic inversion centre. The CoII ion is octahedrally coordinated by two 6‐methylpyridine‐3‐carboxylate ligands in axial positions [Co—O = 2.0621 (9) Å] and by four water molecules in the equatorial plane [Co—O = 2.1169 (9) and 2.1223 (11) Å]. There are also four uncoordinated water molecules. The 6‐methylpyridine‐3‐carboxylate ligands are bound to the CoII ion in a monodentate manner through a carboxylate O atom. There is one strong intramolecular O—H...O hydrogen bond, and six strong intermolecular hydrogen bonds of type O—H...O and one of type O—H...N in the packing, resulting in a complex three‐dimensional supramolecular structure.  相似文献   

10.
《Polyhedron》2002,21(9-10):963-967
Interaction of cobalt(II) ions and sodium carbacylamidophosphates Na(L) (HL=PhC(O)NHP(O)(NR2)2; where NR2 are morpholyl, HL1; NMe2, HL2; NEt2, HL3) in methanol solution afforded polynuclear alkoxo complexes [Co4{L1}3(OCH3)4(OH)(H2O)5·3H2O] 1 and [Co4{L}4(OCH3)4(CH3OH)4] (L=L2 2, L3 3). Data of spectral and TGA studies are presented. Coordination compounds 1 and 3 have been characterized by means of X-ray diffraction. Both the structures consist of tetranuclear cubane alkoxo clusters with methoxide ions bridging three metal centers (CoO 2.068(3)–2.093(4) Å) and phosphorylic ligands coordinated in a bidentatechelate fashion via the carbonyl oxygen atoms (CoO 1: 2.050(2); 3: 2.031(4) Å) and the phosphoryl groups (2.093(2) and 2.106(4) Å). Isolation of these cubane alkoxo complexes is an important proof for close resemblance in behavior of carbacylamidophosphate systems and β-diketonates towards transition metal ions.  相似文献   

11.
Summary The title complexes [ML2]n+=CoIII, CuII, NiII; L=1-thia-4,7-diazacyclononane-S-oxide) have been prepared and characterized spectroscopically. The sulphoxide group is coordinated through the oxygen atom and the complexes have atrans-O,O geometry. The nickel(II) complex of bis(2-amino-ethyl)sulphoxide has also been studied.  相似文献   

12.
The thermally-stable cobalt(II) dialkyl compound CoR2 [R = C(SiMe3)2C5H4N-2] (1) has been prepared by reaction of [{LiR}2] with cobalt(II) chloride in ether. An X-ray structural study has revealed a centrosymmetric molecular skeleton (for two nearly identical independent molecules) in which a pair of sterically-hindered, functionalized pyridine ligands R are trans-chelated to the central planar four-coordinate cobalt(II) atom, with mean CoCα and CoN distances of 2.094(6)Å and 1.919(4) Å respectively, and a CαCoN angle of 69.6(2)°.  相似文献   

13.
The coordination compound [Co(L)(Mal)(H2O)2]H2O (I) (L is benzhydrazide, H2Mal is malonic acid) has been synthesized and studied by IR spectroscopy, thermogravimetry, and X-ray diffraction. Crystals are triclinic, a = 7.610(4) Å, b = 7.854(2) Å, c = 12.751(2) Å, α = 75.12(3)°, β = 88.01(3)°, γ = 80.26(3)°, Z = 2, space group \(P\bar 1\). The structure is molecular. The Co2+ atom has a distorted octahedral coordination. The Co-O and Co-N bond lengths are 2.031-2.129(4) and 2.157(5) Å, respectively. The endocyclic O1Co1N1 bond angles are 77.3(2)° and 90.0(2)° in the five- and six-membered chelate rings, respectively. Molecules of complex I are linked via a great number of hydrogen bonds. The C…C contacts between phenyl rings additionally strengthen the structure.  相似文献   

14.
Crystalline cesium nitratometalates(II), Cs2[M(NO3)4] (M = Mn ( I ), Co ( II ), Ni ( III ), and Zn ( IV )) were synthesized from M(NO3)2 · n H2O and CsNO3 by heating at 80–120 °C over 10–12 h. According to X-ray crystal structure analysis, the compounds are built from Cs+ cations and [M(NO3)4]2– anions. The latter differ by the type of metal coordination: a dodecahedron for Mn in I (CN = 8, rMn–O 2.24–2.37 Å), a seven coordination for Co in II (CN = 4 + 3, rCo–O 2.03–2.16 Å and 2.21–2.35 Å) and a tetrahedral distorted dodecahedron for Zn in IV (CN = 4 + 4, rZn–O 1.98–2.15 Å and 2.38–2.72 Å). Ni atom in III has a distorted octahedral NiO6 environment provided by two unidentate and two bidentate NO3 groups with Ni–O distances of 2.01–2.14 Å. The differences in metal coordination are discussed in terms of valence electron configurations, ionic radii, and the packing effects.  相似文献   

15.
Three new double complex compounds of the following type were obtained: [CoThio 4][Co(SCN)4], [NiThio 4][Ni(SCN)4] and (CuThio 4) (CuCo(SCN)4). The melting points of the compounds were determined, and the molecular weight of the first. The IR-spectra were studied and the metal-ligand bond interpreted. It was shown that the metal-thiourea bond in all compounds is formed via the sulphur atom. In the complex anion of the first and second compounds Co(II) and Ni(II) are coordinated with SCN through the nitrogen atom. In the third, more complicated compound, Cu(II) is coordinated to SCN through the sulphur atom, and Co(II) through the nitrogen atom, a bridging bond being formed.  相似文献   

16.
The crystal structure of a centrosymmetric dinuclear nickel(II) complex, formed from the reaction of bis(L-alaninato)nickel(II) with formaldehyde and methylamine, shows two bridging 2,4,8,10-tetramethyl-5-oxido-5′-carboxylato-2λ5,4,8,10-tetraazaspiro[5.5]undec-2-en(234-del)-ylium ligands, L, and two formato ligands; each nickel atom exists in a trans-N2O4 octahedral geometry with an average (μ-O)–Ni distance of 2.033(1)?Å and Ni···Nii distance of 2.894(1)?Å. Formation of L implicates an unprecedented deamination step involving activation of both the α-carbon and the α-methyl hydrogen atoms of the L-alaninato moiety.  相似文献   

17.
A novel Zn(II) coordination polymer [Zn2(phen)2]L4·3H2O(1) is synthesized by the reaction of Zn(NO3)2, Phen(1,10-phenanthroline), and L(2-mercaptonicotinic acid) at room temperature and structurally characterized by X-ray single crystal diffraction along with IR spectra and elemental analysis. Title complex 1 belongs to the triclinic system with the space group (P-1), a = 10.9373(11) Å, b = 11.6201(12) Å, c = 13.1371(14) Å; α = 116.100(1)°, β = 97.717(2)°, γ = 108.652(2)°, V = 1344.4(2) Å3; Z = 2, ρcalc = 1.596 g·cm?3, F(000) = 664, R 1 = 0.0708 and wR 2 = 0.1823 independent reflections for 18523 observed ones (I > 2σ(I)), and the zinc atom is rendered five-coordinated in a distorted tetragonal pyramid coordination geometry by two nitrogen atoms from the phen molecule, two oxygen atoms from two L molecules, and an oxygen atom from the H2O molecule. Complex 1 forms a 1D chain by O-H…O hydrogen bonds from free-water, while the 2D layer structure is formed by C-H…O hydrogen bonds through the L ligand of adjacent chains. These compounds further result in a 3D network structure by the intermolecular π…π stacking interaction of the neighbouring layers.  相似文献   

18.
A monomeric complex [Co(Im)2(O2CMe)2] (1) and a novel aquabridged dimeric complex [Co2(μ‐H2O)(μ‐CMe)2(Im)4‐(O2CMe)2] (2) (Im = imidazole) have been synthesized and characterized. Complexes 1 and 2 coexisted in solution. Pure forms of either complex can be obtained from the same solution by controlling the crystallization conditions. All two complexes possess a carboxylate‐Im‐cobalt(II) triad system analogous to the carboxylate‐histidine‐metal triad systems that have been found in many zinc enzymes and cobalt(II)‐substituted enzymes. In 2, two Co2+ ions are connected by a water molecule in a bridging fashion with Co°Co [0.3687(1) nm], Co—OH2 [0.2159(3) nm], and Co‐OH2‐Co [117.2(3)°], in which the water molecule is further stabilized by two intramolecular hydrogen bonds with the oxygens of the terminal monodentate acetate groups with the distance of O…0 [0.2609(7) nm]. The terminal monodentate acetate groups display quite abnormal geometry due to the strong “pulling effect” on the carboxylates by intermolecular and intramolecular hydrogen bonds. Complex 2 showed weak antiferromagnetic coupling at low temperature with g = 2.22 and J = ?1.60 cm?1.  相似文献   

19.
A series of new 3d metal complexes based on dimethyl pyridin-2-ylcarbamoylphosphoramidate (HL) was synthesized. The compounds with general formula M(HL)2Cl2·nH2O and M(L)2·nH2O (M=Co2+, Cu2+, Ni2+) were characterized by means of single-crystal X-ray analysis and IR spectroscopy. The organic ligands in all complexes are coordinated via oxygen atom of the carbonyl group and nitrogen atom of the heterocycle. The coordination environment of the central atoms is a distorted octahedron. The axial positions in the Co(II) and Ni(II) complexes with deprotonated ligands are occupied by water molecules. The Co(II) and Cu(II) complexes with phosphoryl ligands in a neutral form have different ligands in the axial positions: in the Co(II) complex, the positions are occupied by two water molecules, whereas in the Cu(II) complex, the positions are occupied by two chlorine anions. The structure of HL was experimentally and theoretically obtained by utilizing single-crystal X-ray analysis and DFT calculations. The computationally optimized geometric parameters for HL show a good agreement with the experimental results.  相似文献   

20.
Four new complexes of 2,3,4-trimethoxybenzoic acid anion with manganese(II), cobalt(II), nickel(II) and copper(II) cations were synthesized, analysed and characterized by standard chemical and physical methods. 2,3,4-Trimethoxybenzoates of Mn(II), Co(II), Ni(II) and Cu(II) are polycrystalline compounds with colours typical for M(II) ions. The carboxylate group in the anhydrous complexes of Mn(II), Co(II) and Ni(II) is monodentate and in that of Cu(II) monohydrate is bidentate bridging one. The anhydrous complexes of Mn(II), Co(II) and Ni(II) heated in air to 1273 K are stable up to 505–517 K. Next in the range of 505–1205 K they decompose to the following oxides: Mn3O4, CoO, NiO. The complex of Cu(II) is stable up to 390 K, and next in the range of 390–443 K it loses one molecule of water. The final product of its decomposition is CuO. The solubility in water at 293 K is of the order of 10–3 mol dm–3 for the Mn(II) complex and 10–4 mol dm–3 for Co(II), Ni(II) and Cu(II) complexes. The magnetic moment values of Mn2+, Co2+, Ni2+ and Cu2+ ions in 2,3,4-trimethoxybenzoates experimentally determined in the range of 77–300 K change from 5.64–6.57 μB (for Mn2+), 4.73–5.17 μB (for Co2+), 3.26–3.35 μB (for Ni2+) and 0.27–1.42 μB (for Cu2+). 2,3,4-Trimethoxybenzoates of Mn(II), Co(II) and Ni(II) follow the Curie–Weiss law, whereas that of Cu(II) forms a dimer.  相似文献   

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