Di-, Tetra-, and Hexanuclear Hydroxy-Bridged Copper(II) Cluster Compounds: Syntheses, Structures, and Properties

Li, Xing; Cheng, Deyi; Lin, Jian‐Li; Li, Zhifeng; Zheng, Yue–Qing

doi:10.1021/cg701150q

Cited by 79 publications

(44 citation statements)

References 64 publications

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“….959 Å,a nd an aqua oxygen O1 occupies the axial position with d(Cu-O1) =2.402 Å which is longer than literature reported 2.265 Å [1]. Elongation is due to the Jahn-Teller effect.…”

Section: Discussionmentioning

confidence: 70%

Crystal structure of bis[(μ2-hydroxo)-aqua-(1,10-phenanthroline- N,N')copper(II)] phenylacetate hexahydrate, [Cu(C₁₂H₈N₂)(OH)(H₂O)]₂[C₈H₇O₂]₂ · 6H₂O

Tu¹,

Ren²,

Ju³

et al. 2009

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialDropwise addition of 1.0 ml of Na2CO3 (1 Msolution) to aaqueous solution of CuCl 2.·.2H2O( 0.170 g, 1.0 mmol) in 5.0 ml of H 2 Ogave ablue precipitate, which was separated by centrifugation and washed with water until no Cl anions were detectable in the supernatant. The collected blue precipitate was transferred to amixture solution of ethanol and water (1:1 v/v,10ml), to which 1,10-phenanthroline (phen, 0.198 g, 1.00 mmol) and phenyl-acetic acid (0.136 g, 1.00 mmol) were added successively. The resulting blue solution (pH =7.82) was allowed to stand at room temperature. Blue block-like crystals were grown by slow evaporation for over 7days. DiscussionThe crystal structure of the title compound is composed of a dinuclear cation [Cu(C 12H8N2)(OH)(H2O)]2 2+ ,a na nion (C 8 H 7 O 2 ) 2 2-and six lattice water molecules. The local coordination of copper(II) ion is tetragonal pyramidal. Two nitrogen atoms of phen and two hydroxyl oxygen atoms are located in the equatorial plane of the tetragonal pyramid with 2+ units indicate significant p-p stacking interactions making acontribution to formation of two-dimensional layers with the interplanner distance of neighboring aromatic rings is 3.17 Å.Inthe phenylacetate anion, two oxygen atoms are in acommon plane and six carbon atoms reside in the other plane, the dihedral angle between the being 26.5°. Through extensive hydrogen bonds between the carboxylate oxygen atoms of free phenyl-acetate, m 2 -OH-, guest and coordination water molecules, along with p-p stacking interactions, title compound exhibits at hree-dimensional supramolecular framework.

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“….959 Å,a nd an aqua oxygen O1 occupies the axial position with d(Cu-O1) =2.402 Å which is longer than literature reported 2.265 Å [1]. Elongation is due to the Jahn-Teller effect.…”

Section: Discussionmentioning

confidence: 70%

Crystal structure of bis[(μ2-hydroxo)-aqua-(1,10-phenanthroline- N,N')copper(II)] phenylacetate hexahydrate, [Cu(C₁₂H₈N₂)(OH)(H₂O)]₂[C₈H₇O₂]₂ · 6H₂O

Tu¹,

Ren²,

Ju³

et al. 2009

Zeitschrift Für Kristallographie - New Crystal Structures

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“…The use of simple metal-containing systems with low molecular weight ligands is useful to understand the correlation between magnetic, electronic, and structural properties in more complex systems [5,6]. For this reason, the synthesis of complexes oriented to mimic metal sites of different types of metalloproteins constitutes an important branch in both inorganic and organic chemistry [7,8]. Copper and cobalt are present in adiverse group of metalloenzymes, in which the metal ions are coordinated by N, Oand S atoms.…”

Section: Discussionmentioning

confidence: 99%

Crystal structure of bis(o-acetamidobenzoato-k2:O:O2)-(1,10- phenanthroline-k2:N1:N2)copper(II), Cu(C12H8N2)(C9H8NO3)2

Tan¹,

Li²,

Nie³

et al. 2011

Zeitschrift Für Kristallographie - New Crystal Structures

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Source of materialAmixture of o-acetamidobenzoic acid (0.036 g, 0.2 mmol), copper sulfate (0.025 g, 0.1 mmol) and 1,10-phenanthroline (0.020 g, 0.1 mmol) was dissolved in 15 ml of methanol. The pH value of the resultant mixture was adjusted to about 6.0 -6 .5 by adding three drops of triethylamine solution and the reaction was kept under water-bath condition at 333 Kf or 25 h. Afterwards, the mixture was filtered, and the filtrate was cooled to room temperature slowly. Deep blue single crystals suitable for X-ray diffraction analysis were obtained after fifteen days. Experimental detailsHatoms bound to Catoms were placed in calculted positions and treated as riding on their parent atoms, with d(C-H) =0.95 Å, U iso (H) =1.2 U eq (C) (aromtic) and d(C-H) =0.95 Å, U iso (H) = 1.5 U eq (C) (methyl). Hatoms attached to Natom was initially located in adifference Fourier map and restrained with d(N-H) = 0.88 Å and U iso(H) =1.2 Ueq(N). DiscussionThe study of the structural, spectroscopic, and electronic properties of metal centers present in biological systems is crucial to understand their role in nature [1,2]. These centers are often modeled by using small molecules containing donor atoms that reproduce the coordination around the metal ion [3,4]. The use of simple metal-containing systems with low molecular weight ligands is useful to understand the correlation between magnetic, electronic, and structural properties in more complex systems [5,6]. For this reason, the synthesis of complexes oriented to mimic metal sites of different types of metalloproteins constitutes an important branch in both inorganic and organic chemistry [7,8]. Copper and cobalt are present in adiverse group of metalloenzymes, in which the metal ions are coordinated by N, Oand S atoms. The crystal structure of the title complex contains a[ Cu(1,10-phen)(C 9 H 8 NO 3 ) 2 ]unit. The copper(II) ion is coordinated by two nitrogen atoms from one 1,10-phenanthroline molecule, four oxygen atoms from two o-acetamidobenzoate anions, forming a distorted octahedron with O1 and O1A at the axial positions and O2, O2A, N1 and N1A in the equatorial plane. The bond angle of O1-Cu1-O1A is 133.05°.Atthe equatorial plane, the bond angles N1-Cu1-N1A, N1A-Cu1-O2A, O2A-Cu1-O2 and O2-Cu1-N1 are 81.3(2)°,9 2.9(1)°,9 3.3(1)°and 92.9(1)°,r espectively, with the sum of 360.28°.The bond length Cu1-O1 is 2.648(2) Å,indicating weak coordination bonds between the carbonyl oxygen atoms of o-carboxylaminobenzoate and the copper ion [8]. In the complex, the coordinated carbonyl oxygen atoms and the nitrogen atoms of o-acetamidobenzoate ligands are linked by strong hydrogen bonds: d(N8-H8···O1) =1 .940 Å, ∠N8-H8···O1= 139.0°.T here exist weak hydrogen bonding interactions betweenthe o-acetamidobenzoate ligands and 1,

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“…2. ORTEP view of the molecular structure of Cu(phen)(H 2 O)(fba) 2 with displacement ellipsoids at the 45 % probability level and atom labeling. The formyl oxygen atoms were found to be twofold disordered.…”

Section: Description Of the Crystal Structurementioning

confidence: 99%

“…However, only two derivatives substituted by a formyl group are known so far, both based on p-formylbenzoic acid (Hfba) [18,19] in an ethanolic aqueous solution yielded Cu(phen)(H 2 O)(fba) 2 . Slow evaporation of the resulting solution led to the crystallization of the title compound.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Crystal Structure and Magnetic Properties of a Copper(II) p-Formylbenzoate Complex

Zheng

2012

Zeitschrift Für Naturforschung B

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A new Cu(II) complex was prepared at room temperature from the reaction of p-formylbenzoic acid, phenanthroline, CuCl 2 ·2H 2 O, and NaOH under ethanolic aqueous conditions. The complex has been characterized by X-ray diffraction, IR spectroscopy, TG-DTA analyses, and magnetic measurements. Single-crystal X-ray diffraction analysis indicated that the complex crystallizes in the triclinic space group P1 with the cell dimensions a = 7.875(2), b = 10.724(2), c = 15.317(3)Å, α = 102.65(3), β = 93.71(3), γ = 107.64(3) • . The Cu atoms are in the environment of distorted CuN 2 O 3 tetragonal pyramids. These discrete complex molecules are packed through intermolecular π···π-stacking interactions and C-H···O hydrogen bonds forming a supramolecular structure. The title complex obeys the Curie-Weiss law with a Curie constant C = 0.53 cm 3 K mol −1 and a Weiss constant θ = − 0.27 K. The shape of the χ m T curve is characteristic of weak ferromagnetic interactions between the Cu(II) centers from 300 to 7 K, while there are weak antiferromagnetic interactions below 7 K.

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Di-, Tetra-, and Hexanuclear Hydroxy-Bridged Copper(II) Cluster Compounds: Syntheses, Structures, and Properties

Cited by 79 publications

References 64 publications

Crystal structure of bis[(μ2-hydroxo)-aqua-(1,10-phenanthroline- N,N')copper(II)] phenylacetate hexahydrate, [Cu(C₁₂H₈N₂)(OH)(H₂O)]₂[C₈H₇O₂]₂ · 6H₂O

Crystal structure of bis[(μ2-hydroxo)-aqua-(1,10-phenanthroline- N,N')copper(II)] phenylacetate hexahydrate, [Cu(C₁₂H₈N₂)(OH)(H₂O)]₂[C₈H₇O₂]₂ · 6H₂O

Crystal structure of bis(o-acetamidobenzoato-k2:O:O2)-(1,10- phenanthroline-k2:N1:N2)copper(II), Cu(C12H8N2)(C9H8NO3)2

Synthesis, Crystal Structure and Magnetic Properties of a Copper(II) p-Formylbenzoate Complex

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Di-, Tetra-, and Hexanuclear Hydroxy-Bridged Copper(II) Cluster Compounds: Syntheses, Structures, and Properties

Cited by 79 publications

References 64 publications

Crystal structure of bis[(μ2-hydroxo)-aqua-(1,10-phenanthroline- N,N')copper(II)] phenylacetate hexahydrate, [Cu(C12H8N2)(OH)(H2O)]2[C8H7O2]2 · 6H2O

Crystal structure of bis[(μ2-hydroxo)-aqua-(1,10-phenanthroline- N,N')copper(II)] phenylacetate hexahydrate, [Cu(C12H8N2)(OH)(H2O)]2[C8H7O2]2 · 6H2O

Crystal structure of bis(o-acetamidobenzoato-k2:O:O2)-(1,10- phenanthroline-k2:N1:N2)copper(II), Cu(C12H8N2)(C9H8NO3)2

Synthesis, Crystal Structure and Magnetic Properties of a Copper(II) p-Formylbenzoate Complex

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Crystal structure of bis[(μ2-hydroxo)-aqua-(1,10-phenanthroline- N,N')copper(II)] phenylacetate hexahydrate, [Cu(C₁₂H₈N₂)(OH)(H₂O)]₂[C₈H₇O₂]₂ · 6H₂O

Crystal structure of bis[(μ2-hydroxo)-aqua-(1,10-phenanthroline- N,N')copper(II)] phenylacetate hexahydrate, [Cu(C₁₂H₈N₂)(OH)(H₂O)]₂[C₈H₇O₂]₂ · 6H₂O