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1.
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   

2.
Three metal-organic frameworks, [Eu(C10H6N3O5)3(H2O)2]?·?H2O (1), [Tb(C10H6N3O5)3(H2O)2]?·?H2O (2), and [Cd(C10H6N3O5)2Cl2] (3) based on T-shaped tripodal ligands 3-(4,5-dicarboxy-1H-imidazol-2-yl)pyridine-1-oxide and 4-(4,5-dicarboxy-1H-imidazol-2-yl)pyridine-1-oxide (H3DCImPyO), have been synthesized by the hydrothermal method and characterized by elemental analysis, IR, and single-crystal X-ray structure analysis. The diverse coordination modes of H3DCImPyO ligands have afforded the three compounds. Complexes 1 and 2 are isomers and the Ln (Ln?=?Eu or Tb) atoms have coordination number eight with a distorted square prism geometry. The partly deprotonated H2DCImPyO? ligands display three different coordination modes to link Ln (Ln?=?Tb or Eu) into 1-D double chains. In 3, Cd(II) lies on an inversion center and displays a slightly distorted octahedral coordination. All three compounds exhibit strong fluorescent emissions in the solid state at room temperature.  相似文献   

3.
Schiff bases are considered `versatile ligands' in coordination chemistry. The design of polynuclear complexes has become of interest due to their facile preparations and varied synthetic, structural and magnetic properties. The reaction of the `ligand complex' [CuL] {H2L is 2,2′‐[propane‐1,3‐diylbis(nitrilomethanylylidene)]diphenol} with Ni(OAc)2·4H2O (OAc is acetate) in the presence of dicyanamide (dca) leads to the formation of bis(dicyanamido‐1κN1)bis(dimethyl sulfoxide)‐2κO,3κO‐bis{μ‐2,2′‐[propane‐1,3‐diylbis(nitrilomethanylylidene)]diphenolato}‐1:2κ6O,O′:O,N,N′,O′;1:3κ6O,O′:O,N,N′,O′‐dicopper(II)nickel(II), [Cu2Ni(C17H16N2O2)2(C2N3)2(C2H6OS)2]. The complex shows strong absorption bands in the frequency region 2155–2269 cm−1, which clearly proves the presence of terminal bonding dca groups. A single‐crystal X‐ray study revealed that two [CuL] units coordinate to an NiII atom through the phenolate O atoms, with double phenolate bridges between CuII and NiII atoms. Two terminal dca groups complete the distorted octahedral geometry around the central NiII atom. According to differential thermal analysis–thermogravimetric analysis (DTA–TGA), the title complex is stable up to 423 K and thermal decomposition starts with the release of two coordinated dimethyl sulfoxide molecules. Free H2L exhibits photoluminescence properties originating from intraligand (π–π*) transitions and fluorescence quenching is observed on complexation of H2L with CuII.  相似文献   

4.
Two organic–inorganic hybrid salts, tris(2-amino-4,6-dimethylpyridinium) tris(oxalato)ferrate(III), (C7H11N2)3[Fe(C2O4)3] (1), and tris(4-dimethylaminopyridinium) tris(oxalato)ferrate(III) tetrahydrate, (C7H11N2)3[Fe(C2O4)3]·4H2O (2), have been synthesized and characterized by elemental and thermal analyses, IR spectroscopy, single-crystal X-ray diffraction, and SQUID magnetometry. Compounds 1 and 2 crystallize in triclinic P-1 and monoclinic C2/c space groups, respectively. Each compound contains the anionic complex [Fe(C2O4)3]3- in which the central metal is six-coordinate in a slightly distorted octahedron defined by three chelating oxalate(2-) ligands. The two substituted pyridinium cations are isomers. However, due to the great steric hindrance provided by the bulky cation, 2-amino-4,6-dimethylpyridinium, only the 4-dimethylaminopyridinium cation, the smallest of this series, led to formation of 2 with enough vacant spaces to be occupied by four solvent water molecules. In the crystals, cations and anions are connected via hydrogen-bonds of the types N–H?O in 1 and N–H?O and O–H?O in 2, with π–π stacking interactions between the pyridine rings stabilizing the 3-D framework. The thermal studies confirmed the anhydrous character of salt 1 and the presence of water molecules in salt 2. The magnetic susceptibility measurements in the 2–300 K temperature range revealed weak antiferromagnetic coupling in the two salts.  相似文献   

5.
[Ni3(C13H9N2O)5(CH3OH)2] (1) and [Cd(C12H8N3)3] (2) were synthesized in methanol and characterized by elemental analyses, IR spectra, and X-ray diffraction. Complex 1 is trinuclear with three unsymmetric Ni(II)'s having different coordinated environments bridged by four oxygen atoms from five ligands. Intermolecular antiferromagnetic interactions were observed in 1. Complex 2 is mononuclear with Cd(II) six-coordinate by six nitrogen atoms from three bidentate HPBM anions. Complex 2 shows emission maxima in the blue region.  相似文献   

6.
Two new mononuclear Ni(II) complexes, [Ni(C10H12O2N2)2(C5H5N)2](NO3)2 (1) and [Ni(C10H12O2N2)2(H2O)2](NO3)2 (2), have been synthesized and characterized by elemental analysis, infrared, UV-Vis spectroscopy, and single-crystal X-ray diffraction. The coordination geometry around each Ni(II) can be described as an octahedron with each Ni(II) coordinated to two imino nitrogens, two carbonyl oxygens, and two solvent molecules (pyridine for 1 and water for 2). In the synthesis, the original ligand changes from o-carboxybenzaldehyde salicyloylhydrazone (C15H12O4N2) into acetone salicyloylhydrazone (C10H12O2N2). The thermal stability of the complexes at three different heating rates (β = 5, 10, and 15°C min?1) show that all the complexes exhibit three thermal decomposition stages and their thermal stability is 1 > 2. Complexes 1 and 2 both display DNA binding ability, ascertained by UV-Vis titration.  相似文献   

7.
The complexes [2‐(1H‐imidazol‐4‐yl‐κN3)ethylamine‐κN]bis(tri‐tert‐butoxysilanethiolato‐κS)cobalt(II), [Co(C12H27O3SSi)2(C5H9N3)], and [2‐(1H‐imidazol‐4‐yl‐κN3)ethylamine‐κN]bis(tri‐tert‐butoxysilanethiolato‐κS)zinc(II), [Zn(C12H27O3SSi)2(C5H9N3)], are isomorphous. The central ZnII/CoII ions are surrounded by two S atoms from the tri‐tert‐butoxysilanethiolate ligand and by two N atoms from the chelating histamine ligand in a distorted tetrahedral geometry, with two intramolecular N—H...O hydrogen‐bonding interactions between the histamine NH2 groups and tert‐butoxy O atoms. Molecules of the complexes are joined into dimers via two intermolecular bifurcated N—H...(S,O) hydrogen bonds. The ZnII atom in [(1H‐imidazol‐4‐yl‐κN3)methanol]bis(tri‐tert‐butoxysilanethiolato‐κ2O,S)zinc(II), [Zn(C12H27O3SSi)2(C4H6N2O)], is five‐coordinated by two O and two S atoms from the O,S‐chelating silanethiolate ligand and by one N atom from (1H‐imidazol‐4‐yl)methanol; the hydroxy group forms an intramolecular hydrogen bond with sulfur. Molecules of this complex pack as zigzag chains linked by N—H...O hydrogen bonds. These structures provide reference details for cysteine‐ and histidine‐ligated metal centers in proteins.  相似文献   

8.
Two compounds of disphosphopentamolybdate(VI) with the formulae (C4H14N2O)3- [P2Mo5O23]?·?3H2O (1) and (C4H14N2O)5(NH4)2[P2Mo5O23]2?·?5H2O (2) have been synthesized by a simple, fast and efficient microwave method, and their crystal structures and spectroscopic properties have been studied. The heteropoly anion [P2Mo5O23]6? has a known structure built of five MoO6 octahedra and two PO4 tetrahedra. The MoO6 octahedra form a pentagonal ring by sharing four edges and one corner and the PO4 tetrahedra are attached to one side of the ring by three oxygen atoms. The most interesting feature of compound 1 is its extensive framework based on a one-dimensional zigzag chain. In compound 2, a more extensive and complicated framework of hydrogen bonds joins the anions, organic cations and water molecules together.  相似文献   

9.
The compound Rb3[NbO(C2O4)3]⋅2H2O (1) has been synthesized by two different methods and its exact chemical composition established. The niobium atom is heptacoordinated by oxygen atoms forming a distorted pentagonal bipyramid. Inspite of some similarities, the structure of 1 is not isotypic with the structure of (NH4)3[NbO(C2O4)3]⋅H2O.  相似文献   

10.
The title complexes, (C12H8N2) ? [La(C7H3NO5)(C7H4NO5) ? 3H2O] ? 1.75H2O (1), (C12H8N2) ? [Pr(C7H3NO5)(C7H4NO5) ? 3H2O] ? 2H2O (2), (C12H8N2)[Nd(C7H3NO5)(C7H4NO5) ? 3H2O] ? 2.25H2O (3), and (C12H8N2) ? [Fe(C7H3NO5)(C7H4NO5)] ? 2H2O (4), were synthesized and characterized by single-crystal X-ray diffraction. The crystal structures of 13 reveal that they are isomorphous, among which the metal atoms are all nine-coordinate with distorted tricapped trigonal prismatic coordination geometries. The Fe is six-coordinate with a distorted octahedron by two chelidamic acid ligands in 4. Complexes 14 are formed into 3-D networks by H-bonds and π–π stacking interactions. The fluorescence spectra of 13 were investigated and all exhibit strong luminescence.  相似文献   

11.
Yellow–orange tetraaquabis(3‐cyano‐4‐dicyanomethylene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olato‐κN3)cadmium(II) dihydrate, [Cd(C8HN4O2)2(H2O)4]·2H2O, (I), and yellow tetraaquabis(3‐cyano‐4‐dicyanomethylene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olato‐κN3)cadmium(II) 1,4‐dioxane solvate, [Cd(C8HN4O2)2(H2O)4]·C4H8O2, (II), contain centrosymmetric mononuclear Cd2+ coordination complex molecules in different conformations. Dark‐red poly[[decaaquabis(μ2‐3‐cyano‐4‐dicyanomethylene‐5‐oxo‐4,5‐dihydro‐1H‐pyrrol‐2‐olato‐κ2N:N′)bis(μ2‐3‐cyano‐4‐dicyanomethylene‐1H‐pyrrole‐2,5‐diolato‐κ2N:N′)tricadmium] hemihydrate], [Cd3(C8HN4O2)2(C8N4O2)2(H2O)10]·0.5H2O, (III), has a polymeric two‐dimensional structure, the building block of which includes two cadmium cations (one of them located on an inversion centre), and both singly and doubly charged anions. The cathodoluminescence spectra of the crystals are different and cover the wavelength range from UV to red, with emission peaks at 377 and 620 nm for (III), and at 583 and 580 nm for (I) and (II), respectively.  相似文献   

12.
Naphthaldimines containing N2O2 donor centers react with platinum(II) and (IV) chlorides to give two types of complexes depending on the valence of the platinum ion. For [Pt(II)], the ligand is neutral, [(H2L1)PtCl2]·3H2O (1) and [(H2L3)2Pt2Cl4]·5H2O (3), or monobasic [(HL2)2Pt2Cl2]·2H2O (2) and [(HL4)2Pt]·2H2O (4). These complexes are all diamagnetic having square-planar geometry. For [Pt(IV)], the ligand is dibasic, [(L1)Pt2Cl4(OH)2]·2H2O (5), [(L2)Pt3Cl10]·3H2O (6), [(L3)Pt2Cl4(OH)2]·C2H5OH (7) and [(L4)Pt2Cl6]·H2O (8). The Pt(IV) complexes are diamagnetic and exhibit octahedral configuration around the platinum ion. The complexes were characterized by elemental analysis, UV-Vis and IR spectra, electrical conductivity and thermal analyses (DTA and TGA). The molar conductances in DMF solutions indicate that the complexes are non-ionic. The complexes were tested for their catalytic activities towards cathodic reduction of oxygen.  相似文献   

13.
《Journal of Coordination Chemistry》2012,65(16-18):2569-2583
Abstract

Two copper(II) coordination complexes, formulated as [Cu(tmen)(Clba)2] (1) and [Cu(tmen)(Hsal)2·H2O] (2) (where tmen?=?N,N,N′,N′-tetramethyl ethylenediamine (C6H16N2), Clba1? = 2-chlorobenzoate (C7H4ClO21?), and Hsal1? (C7H5O31? = monoanion of o-hydroxybenzoic acid (salicylic acid)), have been synthesized and characterized by elemental combustion analysis, spectroscopic techniques, thermal studies, and single crystal X-ray analyses. Complex 1 consists of two distinct monomeric units in which the coordination environment around the central copper(II) ion is a distorted octahedron with a CuN2O4 chromophore, constituted by a chelating tmen molecule, and two 2-chlorobenzoate1? anions coordinated through their carboxylate-O atoms in an asymmetrical bidentate fashion. Complex 2 is also a monomer and consists of an CuN2O3 chromophore, in which tmen is coordinated to Cu(II) through its two N atoms in a chelating bidentate fashion, and an aqua-O and the two o-hydroxybenzoate1? (HSal1?) anions are coordinated through one of their carboxylate-O atoms in a monodentate mode, forming a square pyramidal structure. Hydrogen bonding interactions especially of O–H…O, N–H…O, and C–H…Cl types interweave monomeric units and stabilize the overall crystal structures in both complexes. Thermal analysis and antibacterial activities of 1 and 2 against various bacterial strains were also investigated.  相似文献   

14.
Three coordination polymers, {[Co(C10H5N3O5)(H2O)2]·H2O}n (1), {[Mn3(C10H5N3O5)2Cl2(H2O)6]·2H2O}n (2), and {[Cu3(C10H4N3O5)2(H2O)3]·4H2O}n (3), based on a T-shaped tripodal ligand 4-(4,5-dicarboxy-1H-imidazol-2-yl)pyridine 1-oxide (H3DCImPyO), were synthesized under hydrothermal conditions. The polymers showed diverse coordination modes, being characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray structure analysis. In 1, the HDCImPyO2? generated a 1-D chain by adopting a μ2-kN, O : kN′, O′ coordination mode to bridge two Co(II) ions in two bis-N,O-chelating modes. In 2, the HDCImPyO2? adopted a μ3-kN, O : kO′, O′′ : O′′′ coordination mode to bridge two crystallographically independent Mn(II) ions, forming a 2-D hcb network with {63} topology. In 3, by adopting μ4-kN, O : kO′, O′′ : kN′′, O′′′ : O′′′′ coordination, DCImPyO3? bridged three crystallographically independent Cu(II) ions to form a 3-D framework having the stb topology.  相似文献   

15.
The title compound, [Mn(C12H8N2)2(H2O)2](C4H4O4S)·[Mn(C4H4O4S)(C12H8N2)2]·13H2O, contains one dianion of thio­diglycolic acid (tdga2−) and two independent man­ganese(II) moieties, viz. [Mn(phen)2(H2O)2]2+ and [Mn(tdga)(phen)2], where phen is 1,10‐phenanthroline. The MnII atoms are octahedrally coordinated by four N atoms of two bidentate phen ligands [Mn—N = 2.240 (2)–2.3222 (19) Å] and either two water O atoms or two tdga carboxyl O atoms [Mn—O = 2.1214 (17)–2.1512 (17) Å]. The tdga ligand chelates as an O,O′‐bidentate ligand, forming an eight‐membered ring with one Mn atom. The free tdga2− dianion is hydrogen bonded to an [Mn(phen)2(H2O)2]2+ ion, with O⋯O distances of 2.606 (2) and 2.649 (2) Å. The crystal structure is further stabilized by an extensive network of hydrogen bonds involving 13 water mol­ecules.  相似文献   

16.
The crystal structures of two (hexafluoroacetylacetonato)copper(II) complexes with 3-imidazoline nitroxide radicals, [Cu(C5HF6O2)2]3 (C14H19N2O)2 (I) and [Cu(C5HF6O2)2]3 (C13H17N2O3)2 (II), have been determined. The compounds are triclinic (PI, Z=1) with a=8.730(2), b=10.357(2), c=21.996(5) Å, α=103.24(2), β=94.03(2), γ=95.04(2)0, V=1920(1) Å3 for I and a=8.679(2), b=14.769(4), c=15.368(4) Å, α=85.58(2), β=96.25(1), γ=104.60(1)0, V=1893(1) Å3 for II. Complexes I and II are molecular. The trinuclear molecules are centrosymmetric relative to the Cu(1) atom. The coordination polyhedron of Cu(1) is a square bipyramid formed by the O atoms of the hfac anions and nitroxide radicals (average Cu?Ohfac 1.92(1) for I and 1.93(1) Å for II; Cu?ON?O 2.47(1) for I and 2.56(1) Å for II). The coordination polyhedron of Cu(2) is a trigonal bipyramid formed by the O atoms of the hfac anions (Cu?Ohfac 1.91(1)–2.12(1) for I and 1.91(1)–2.09(1) Å for II) and an imine N atom of the radical (Cu(2)?N(2) 2.00(1) for I and 2.03(1) Å for II). The molecules are linked by van der Waals forces.  相似文献   

17.
In poly[[bis(μ‐4,4′‐bi‐1H‐pyrazole‐κ2N2:N2′)bis(3‐carboxyadamantane‐1‐carboxylato‐κO1)cobalt(II)] dihydrate], {[Co(C12H15O4)2(C6H6N4)2]·2H2O}n, (I), the Co2+ cation lies on an inversion centre and the 4,4′‐bipyrazole (4,4′‐bpz) ligands are also situated across centres of inversion. In its non‐isomorphous cadmium analogue, {[Cd(C12H15O4)2(C6H6N4)2]·2H2O}n, (II), the Cd2+ cation lies on a twofold axis. In both compounds, the metal cations adopt an octahedral coordination, with four pyrazole N atoms in the equatorial plane [Co—N = 2.156 (2) and 2.162 (2) Å; Cd—N = 2.298 (2) and 2.321 (2) Å] and two axial carboxylate O atoms [Co—O = 2.1547 (18) Å and Cd—O = 2.347 (2) Å]. In both structures, interligand hydrogen bonding [N...O = 2.682 (3)–2.819 (3) Å] is essential for stabilization of the MN4O2 environment with its unusually high (for bulky adamantanecarboxylates) number of coordinated N‐donor co‐ligands. The compounds adopt two‐dimensional coordination connectivities and exist as square‐grid [M(4,4′‐bpz)2]n networks accommodating monodentate carboxylate ligands. The interlayer linkage is provided by hydrogen bonds from the carboxylic acid groups via the solvent water molecules [O...O = 2.565 (3) and 2.616 (3) Å] to the carboxylate groups in the next layer [O...O = 2.717 (3)–2.841 (3) Å], thereby extending the structures in the third dimension.  相似文献   

18.

Reaction of freshly-prepared CuCO3, phenanthroline monohydrate and maleic acid in CH3OH/H2O(1 : 1 v/v) at pH=2.13 yielded diaqua(1,10-phenanthroline-N,N')hydrogenmaleatocopper(II) hydrogenmaleate monohydrate, [Cu(phen)(H2O)2(C4H3O4)](C4H3O4)(H2O), which consists of [Cu(phen)(H2O)2(C4H3O4)]+ complex cations, hydrogenmaleate anions and lattice H2O molecules. Within the complex cations, the Cu atoms are each square-pyramidally coordinated by two N atoms of one chelating phen ligand and three O atoms of two H2O molecules and one hydrogenmaleato ligand with one H2O molecule at the apical position (d(Cu-N) = 2.001, 2.009 Å, equatorial d(Cu-O) = 1.966 Å and axial d(Cu-O) = 2.235 Å). Through hydrogen bonding, the complex cations, hydrogenmaleate anions and lattice H2O molecules are assembled into 1D chains, which are held together by weak Cu···O interactions (3.139 Å) to form corrugated 2D layers. Significant π-π stacking interactions between neighboring phen ligands leads to supramolecular assembly of the 2D layers. Over the temperature range 5-300 K, the complex obeys the Currie-Weiss law with an effective magnetic moment of 1.78 BM at room temperature.  相似文献   

19.
pH titration shows that 1 : 1 : 1 mixed-ligand complexes are formed in the systems palladium(II)-Cyt-Glu-H2O (loggB = 19.73) and palladium(II)-Cyt-Lys-H2O (logβ = 16.20). Complexes Pd(C5H5N5)(C5H8NO4)Cl, Pd(C5H5N5)(C6H13N2O2)Cl, Pd(C4H5N3O)(C6H13N2O2)Cl, and Pd(C4H5N3O)(C5H8NO4)Cl are synthesized and characterized by chemical analysis, X-ray powder diffraction, and thermogravimetry. The coordination mode of amino acids, cytosine, and adenine to the palladium(II) ion is determined.  相似文献   

20.
Rare homodinuclear Co (II) complex [Co2(L)NO3] ( 1 ) and helical centrosymmetric homotetranuclear Cu (II) complex [Cu4(L)2(H2O)2]·2ClO4 ( 2 ), have been synthesized by a newly explored bis (salamo)-like tetraoxime ligand (H3L) with Co (NO3)2·6H2O and Cu (ClO4)2·6H2O, respectively, and characterized by elemental analyses, IR, UV–Vis spectroscopy and single crystal X-ray crystallography. X-ray crystallographic studies indicate that the two Co (II) atoms (Co1 and Co2) in complex 1 have different N2O4 and N2O3 coordination spheres, and distorted octahedral (Co1) and slightly distorted triangular bipyramidal (Co2) geometries, while Cu (II) atoms in complex 2 have also two different N2O4 (Cu1) and N2O3 (Cu2) coordination environments, and complex 2 forms a helical centrosymmetric molecule. In addition, supramolecular interactions, Hirshfeld surfaces analyses, antibacterial and fluorescence properties were also investigated in detail.  相似文献   

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