• Title/Summary/Keyword: Distorted Square Pyramidal Geometry

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Structures and Magnetic Properties of Monomeric Copper(II) Bromide Complexes with a Pyridine-Containing Tridentate Schiff Base

  • Kang, Sung Kwon;Yong, Soon Jung;Song, Young-Kwang;Kim, Young-Inn
    • Bulletin of the Korean Chemical Society
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    • v.34 no.12
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    • pp.3615-3620
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    • 2013
  • Two novel copper(II) bromide complexes with pyridine containing Schiff base ligands, $Cu(pmed)Br_2$ and $Cu(pmed)Br_2$ where pmed = N'-((pyridin-2-yl)methylene)ethane-1,2-diamine (pmed) and dpmed = N,N-diethyl-N'-((pyridin-2-yl)methylene)ethane-1,2-diamine (dpmed) were synthesized and characterized using X-ray single crystal structure analysis, optical and magnetic susceptibility measurements. Crystal structural analysis of $Cu(pmed)Br_2$ showed that the copper(II) ion has a distorted square-pyramidal geometry with the trigonality index of ${\tau}=0.35$ and two intermolecular hydrogen bonds, which result in the formation of two dimensional networks in the ab plane. On the other hand, $Cu(pmed)Br_2$ displayed a near square-pyramidal geometry with the value of ${\tau}=0.06$. In both compounds, the NNN Schiff base and one Br atom occupy the basal plane, whereas the fifth apical position is occupied by the other Br atom at a greater Cu-Br apical distance. The reported complexes show $g_{\mid}$ > $g_{\perp}$ > 2.0023 with a $d_{x2-y2}$ ground state and a penta-coordinated square pyramidal geometry. Variable temperature magnetic susceptibility measurements showed that the developed copper(II) complexes follow the Curie-Weiss law, that is there are no magnetic interactions between the copper(II) ions since the Cu--Cu distance is too far for magnetic contact.

Synthesis and Crystal Structures of Copper(II) Complexes with Schiff Base Ligands: [Cu2(acpy-mdtc)2(HBA)(ClO4)]·H2O and [Cu2(acpy-phtsc)2(HBA)]·ClO4

  • Koo, Bon Kweon
    • Bulletin of the Korean Chemical Society
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    • v.34 no.11
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    • pp.3233-3238
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    • 2013
  • Two new Cu(II) complexes, $[Cu_2(acpy-mdtc)_2(HBA)(ClO_4)]{\cdot}H_2O$ (1) (acpy-mdtc- = 2-acetylpyridine S-methyldithiocarbamate and $HBA^-$ = benzilic acid anion) and $[Cu_2(acpy-phtsc)_2(HBA)]{\cdot}ClO_4$ (2) (acpy-$phtsc^-$ = 2-acetylpyridine 4-phenyl-3-thiosemicarbazate) have been synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single crystal X-ray diffraction. The X-ray analysis reveals that the structures of 1 and 2 are dinuclear copper(II) complexes bridged by two thiolate sulfur atoms of Schiff base ligand and bidentate bridging $HBA^-$ anion. For 1, each of the two copper atoms has different coordination environments. Cu1 adopts a five-coordinate square-pyramidal with a $N_2OS_2$ donor, while Cu2 exhibits a distorted octahedral geometry in a $N_2O_2S_2$ manner. For 2, two Cu(II) ions all have a five-coordinate square-pyramidal with a $N_2OS_2$ donor. In each complex, the Schiff base ligand is coordinated to copper ions as a tridentate thiol mode.

Synthesis, Properties, and X-ray Crystal Structure of Copper(II) Complex with Bis[(2-pyridyl)methyl]-2-(2-pyridyl)ethylamine (Bis[(2-pyridyl)methyl]-2-(2-pyridyl)ethylamine 구리(II) 착물의 합성, 성질 및 X-ray 결정구조)

  • Choi, Ki-Young
    • Journal of the Korean Chemical Society
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    • v.51 no.1
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    • pp.31-35
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    • 2007
  • The tripodal copper(II) complex [Cu(pmea)(H2O)](ClO4)2·H2O (1) (pmea = bis[(2-pyridyl)methyl]-2-(2-pyridyl)ethylamine) has been synthesized and structurally characterized by X-ray diffraction method. It crystallizes in the triclinic system P-1 with a = 9.9362(9), b = 15.7299(17), c = 18.0562(11) A, α = 68.760(8), β = 76.331(6), γ = 77.092(9)°, V = 2526.2(4) A3, Z = 2. Each copper atom reveals a distorted square pyramidal with three nitrogen atoms of the pmea ligand and water molecule occupying the basal plane and one nitrogen atom from the pyridine ring according the axial position. The cyclic voltammogram of 1 undergoes reversible one-electron oxidation to the CuIII and reversible one-electron reduction to the CuI.

Structural and Magnetic Properties of Monomeric and Dimeric Copper(II) Complexes with Phenyl-N-[(pyridine-2-yl)methylene]methaneamide

  • Lee, Hong-Woo;Sengottuvelan, Nallathambi;Seo, Hoe-Joo;Choi, Jae-Soo;Kang, Sung-Kwon;Kim, Young-Inn
    • Bulletin of the Korean Chemical Society
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    • v.29 no.9
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    • pp.1711-1716
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    • 2008
  • The reaction of copper(II) chloride with phenyl-N-[(pyridine-2-yl)methylene]methaneamide (ppmma) leads to a new $\mu$ -chloro bridged dimeric [Cu(ppmma)$Cl_2$]$_2$ complex, whereas a reaction of copper(II) bromide with ppmma affords a monomeric Cu(ppmma)$Br_2$ complex. Both complexes have been characterized by X-ray crystallography and electronic absorption spectroscopy. The crystal structural analysis of [Cu(ppmma)$Cl_2$]$_2$ shows that the two Cu(II) atoms are bridged by two chloride ligands, forming a dimeric copper(II) complex and the copper ion has a distorted square-pyramidal geometry ($\tau$ = 0.2). The dimer units are held through a strong intermolecular $\pi-\pi$ interactions between the nearest benzyl rings. On the other hand, Cu(ppmma)Br2 displayed a distorted square planar geometry with two types of strong intermolecular π-π interaction. EPR spectrum of [Cu(ppmma)$Cl_2$]$_2$ in frozen glas s at 77 K revealed an equilibrium between the mononuclear and binuclear species. The magnetic susceptibilities data of [Cu(ppmma)$Cl_2$]$_2$ and Cu(ppmma)$Br_2$ follow the Curie-Weiss law. No significant intermolecular magnetic interactions were examined in both complexes, and magnetic exchange interactions are discussed on the basis of the structural features.

Synthesis and Crystal Structures of Di-nuclear Zinc(II) Diphenate Complexes with 1,10-Phenanthroline and 2,2'-Bipyridine

  • Koo, Bon-Kweon
    • Bulletin of the Korean Chemical Society
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    • v.32 no.8
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    • pp.2617-2622
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    • 2011
  • Two new Zn(II) complexes, $[Zn_2(dpa)_2(phen)_2(H_2O)_2]{\cdot}H_2O$ (1) (dpa = dephenate, phen = 1,10-phenanthroline) and [$Zn_2(dpa)_2(bpy)_2(H_2O)_2$] (2) (bpy = 2,2'-bipyridine) have been synthesized and characterized by elemental analysis, infrared spectroscopy, thermogravimetric analysis, and single crystal X-ray diffraction. The X-ray analysis reveals that the structures of 1 and 2 are dinuclear zinc(II) complexes bridged by dpa dianions, respectively. The zinc ions in 1 exhibit a distorted square pyramidal environments, while the zinc ions in 2 exhibit a trigonal bipyramid geometry. In each complex, the dpa ligand is coordinated to zinc ions as a bis-monodentate.

X-ray Structure and Electrochemical Properties of Ferrocene-Substituted Metalloporphyrins

  • Kim, Jin Won;Lee, Seok U;Na, Yong Hwan;Lee, Gi Pyeong;Do, Yeong Gyu;Jeong, Se Chae
    • Bulletin of the Korean Chemical Society
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    • v.22 no.12
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    • pp.1316-1322
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    • 2001
  • Transition metal complexes of novel mono- and di-ferrocene-substituted porphyrins have been synthesized and characterized by structural and electrochemical methods. The X-ray structures of Mn(FPTTP)Cl and Mn(DFTTP)Cl showed the distorted square pyramidal coordination geometry with syn configuration of chloride and ferrocenyl substituents. The electrochemistry of ferrocene-substituted porphyrins and their metal complexes has been determined to elucidate the ${\pi}-conjugation$ effect of the porphyrin ring. The ferrocenyl group of H2FPTTP underwent a reversible one-electron transfer process at 0.30 V, indicating the good electron donating effect of the phorphyrin ring to the ferrocene substituent. The redox potential of the ferrocenyl subunit and porphyrin ring was affected by the central metal ions of the metalloporphyrins, that is, Zn(II) and Ni(II) made the oxidation of ferrocene much easier and Mn(III) made it harder. The ferrocene subunits of H2DFTTP interacted electrochemically with each other with peak splitting of 0.21 V. The strength of the electrochemical interactions between the two ferrocenyl substituents can be controlled by central metal ions of metalloporphyrins.

Extended Bifurcated Hydrogen Bonds Network Material of Copper(II) Complexes with 2-Dimethylaminomethyl-3-hydroxypyridine: Structures and Magnetic Properties

  • Kang, Sung-Kwon;Lee, Hong-Woo;Sengottuvelan, Nallathambi;Kim, Young-Inn
    • Bulletin of the Korean Chemical Society
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    • v.33 no.1
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    • pp.95-99
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    • 2012
  • Two novel copper(II) complexes, [Cu(dmamhp)$(H_2O)_2(SO_4)]_n$ (1) and [Cu(dmamhp)$(NO_3)_2(H_2O)]{\cdot}H_2O$ (2) [dmamhp = 2-dimethylaminomethyl-3-hydroxypyridine] have been synthesized and structurally characterized by single crystal X-ray diffraction analysis. Compound 1 displays a double one-dimensional chains structure, in which each chain is constituted with the distorted octahedral copper(II) complex bridged through bidentate sulfate ligands resulting in a coordination polymer. The bifurcated hydrogen bonds and $\pi-\pi$ interactions play important roles in the formation of the double chains structure. On the other hand, compound 2 adopts a distorted square pyramidal geometry around copper(II) ion and exists as a discrete monomer. There are intermolecular bifurcated hydrogen bonds and $\pi-\pi$ stacking interactions between the monomeric units. The magnetic properties revealed that the paramagnetic behaviors are dominantly manifested and there are no intermolecular magnetic interactions in both compound 1 and 2.

Structure and Properties of a Nonheme Pentacoordinate Iron(II) Complex with a Macrocyclic Triazapyridinophane Ligand

  • You, Minyoung;Seo, Mi Sook;Kim, Kwan Mook;Nam, Wonwoo;Kim, Jinheung
    • Bulletin of the Korean Chemical Society
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    • v.27 no.8
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    • pp.1140-1144
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    • 2006
  • A macrocyclic ligand, N,N',N'-tribenzyl-2,11,20-triaza[3,3,3](2,6)pyridinophane (BAPP), was used to prepare an iron(II) complex as a nonheme model complex, $[(BAPP)Fe]^{+2}$ (1). X-ray crystallography of a colorless crystal of 1 revealed that BAPP acted as a pentadentate ligand due to geometrical strain for the formation of a six-coordinate iron(II) complex by BAPP. As a result, the iron center revealed a significantly distorted square pyramidal geometry similar to that found in the active site of taurine dioxygenase (tauD). In the reaction of 1 with PhIO, no intermediate was observed in the UV-visible region of spectrometer at low temperatures. Catalytic oxidations of triphenyl phosphine with PhIO at ${-40^{\circ}C}$ revealed that 1 was able to convert triphenyl phosphine to triphenyl phosphine oxide.23; SSOCHKThioanisole was also oxidized to the corresponding methylphenyl sulfoxide under the same conditions.

Template Synthesis of Polyaza Macrocyclic Copper(II) and Nickel(II) Complexes: Spectral Characterization and Antimicrobial Studies

  • Gurumoorthy, P.;Ravichandran, J.;Karthikeyan, N.;Palani, P.;Rahiman, A. Kalilur
    • Bulletin of the Korean Chemical Society
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    • v.33 no.7
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    • pp.2279-2286
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    • 2012
  • The template synthesis of copper(II) and nickel(II) complexes derived from 2,6-diformyl-4-methylphenol with diethylenetriamine or 1,2-bis(3-aminopropylamino)ethane produce the 12-membered $N_3O$ and 17-membered $N_4O$ macrocyclic complexes, respectively. The geometry of the complexes has been determined with the help of electronic and EPR spectroscopic values and found to be five coordinated square pyramidal and, six coordinated distorted tetragonal for 12-membered and 17-membered macrocyclic complexes, respectively. Electrochemical studies of the mononuclear $N_3O$ and $N_4O$ copper(II) complexes show one irreversible oneelectron reduction wave at $E_{pc}=-1.35$ and -1.15 V respectively, and the corresponding nickel(II) complexes show irreversible one-electron reduction wave at $E_{pc}=-1.25$ and -1.22 V, respectively. The nickel(II) complexes show irreversible one-electron oxidation wave at $E_{pa}=+0.84$ and +0.82 V, respectively. All the complexes were evaluated for in vitro antimicrobial activity against the human pathogenic bacteria and fungi.

Coordination of an Amino Alcohol Schiff Base Ligand Toward Cd(II)

  • Mardani, Zahra;Hakimi, Mohammad;Moeini, Keyvan;Mohr, Fabian
    • Journal of the Korean Chemical Society
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    • v.63 no.1
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    • pp.29-36
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    • 2019
  • A potentially tetradentate Schiff base ligand, 2-((2-((pyridin-2-ylmethylene)amino)ethyl)amino)ethan-1-ol (PMAE), and its cadmium(II) complex, [$Cd(PMAE)I_2$] (1), were prepared and characterized by elemental analysis, FT-IR, Raman, $^1H$ and $^{13}C$ NMR spectroscopies and single-crystal X-ray diffraction. In the crystal structure of 1, the cadmium atom has a slightly distorted square-pyramidal geometry and a $CdN_3I_2$ environment in which the PMAE acts as an $N_3$-donor. In the crystal packing of the complex, the alcohol and amine groups of the coordinated ligands participate in hydrogen bonding with iodide ions and form $R^2{_2}(14)$ and $R^2{_2}(8)$ hydrogen bond motifs, respectively. In addition to the hydrogen bonds, the crystal network is stabilized by ${\pi}-{\pi}$ stacking interactions between pyridine rings. The thermodynamic stability of the isolated ligand and its cadmium complex along with their charge distribution patterns were studied by DFT and NBO analysis.