• Title/Summary/Keyword: Distorted octahedron

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Structure and Bonding of Perovskites A($Cu_{1/3}Nb_{2/3}$)$O_3$ (A=Sr, Ba and Pb) and their Series of Mixed Perovskites

  • Park Hyu-Bum;Huh Hwang;Kim Si-Joong
    • Bulletin of the Korean Chemical Society
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    • v.13 no.2
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    • pp.122-127
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    • 1992
  • Some perovskites $A($Cu_{1}3}Nb_{2}3}$)O_3(A=$Sr^{2+}$$, $Ba^{2+}$ and $Pb^{2+}$) and their series of mixed perovskites have been prepared by solid state reaction. Single perovskite phase was obtained in Sr or Ba rich samples, but pyrochlore phase was found in Pb rich samples. The stability of perovskite phase is dependent on the ionicity of bonding as well as the tolerance factor. All the obtained perovskites have tetragonal symmetry distorted by Jahn-Teller effect of $Cu^{2+}$. In the case of $Sr(Cu_{1}3}Nb_{2}3})O_3$, some superlattice lines caused by threefold enlarging of fundamental unit cell were observed. And, the symmetry of B site octahedron and the bonding character of B-O bond have been studied by IR, ESR and diffuse reflection spectroscopy. It appeared that the symmetry and the bonding character are influenced by such factors as the size and the basicity of A cation.

Cr(III)-Tetraaza Macrocyclic Complexes Containing Auxiliary Ligands (Part I); Synthesis and Characterization of Cr(III)-Benzoato and Chlorobenzoato Macrocyclic Complexes

  • Byun, Jong-Chul;Kim, Goo-Cheul;Han, Chung-Hun
    • Bulletin of the Korean Chemical Society
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    • v.25 no.7
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    • pp.977-982
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    • 2004
  • The reaction of $cis-[Cr([14]-decane)(OH_2)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = benzoate(bz) or chlorobenzoate(cbz)} leads to a new compound $[Cr([14]-decane)(bz)_2]ClO_4$ or $[Cr([14]-decane)(cbz)_2]ClO_4$. These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. The crystal structure of $[Cr([14]-decane)(cbz)_2]^+$ was determined. The complex shows a distorted octahedral coordination environment with the macrocycle adopting a folded cis-V conformation. The angle $N_{axial}-Cr-N_{axial}$ deviates by $14.5^{\circ}$ from the ideal value of $180^{\circ}$for a perfect octahedron. The bond angle cis-O-Cr-O between the Cr(III) ion and the two carboxylate oxygen atoms of the monodentate p-chlorobenzoate ligands is close to 90$^{\circ}$. The FAB mass spectra of the $cis-[Cr([14]-decane)(La)_2]ClO_4$ display peaks due to the molecular ions $[Cr([14]-decane)(bz)_2-H]^\;,\;[Cr([14]-decane)(cbz)_2-2H]^$ at m/z 578, 646, respectively.

Crystal Structure of $[Ni(L)](ClO_4)_2$ (L: 2,13-bis(2-pyridylmethyl)-3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,$0^{1.18},0^{7.12}$]docosane) ($[Ni(L)](ClO_4)_2$(L: 2,13-bis(2-pyridylmethyl)-3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,$0^{1.18},0^{7.12}$docosane) 착물의 결정구조)

  • Park, Ki-Young;Suh, Il-Hwan;Kim, Jing-Gyu;Park, Young-Soo
    • Korean Journal of Crystallography
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    • v.10 no.1
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    • pp.88-93
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    • 1999
  • The complex [Ni(L)](ClO4)2 (1) (L=2,13-bis(2-pyridylmethyl)-3,14-dimethyl-2,6,13,17-tetraazatricyclo[14,4,01.1807.12]docosane) has been synthesized and characterized by X-ray crystallography. (1) crystallizes in the triclinic, space group P, with a=10.948(2), b=10.948(2), c=14.911(4) , α=93.73(2), β=93.77(2), γ=99.29(2)o, V=1754.8(7) 3, Z=2, R1(wR2) for 5217 observed reflections of [I>2σ(I)] was 0.048(0.099). The coordination environment around nickel(II) ion shows a distorted octahedron with four secondary and tertially amines of the macrocycle and two nitrogen atoms of pyridylmethyl groups.

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Variation of the Curie Temperature in $BaTiO_3$ Doping $Cd_5(PO_4)_3Cl$ ($BaTiO_3$에서 $Cd_5(PO_4)_3Cl$의 첨가로 인한 Curie 온도변화)

  • Kim, Gwang-Chul
    • Journal of the Semiconductor & Display Technology
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    • v.10 no.1
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    • pp.95-99
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    • 2011
  • $(1-x)BaTiO_3+(x)Cd_5(PO_4)_3Cl$ ceramics were prepared by the conventional ceramic technique, i.e., solid state reaction at high temperature. The concentration of $Cd_5(PO_4)_3C$ was varied from 0.01 to 0.15 mole fraction. In order to study the phase transitions of our ceramics, the Raman scattering spectra were measured as functions of concentration x and temperature. It was found that the soluble limit of $Cd_5(PO_4)_3Cl$ in $BaTiO_3$ was the x=0.05 composition and $BaTiO_3$ phase disappeared above x=0.10. A new phase identified as $Ba_4Ti_3P_2O_{15}$ was detected in all samples of our compositions. The Curie temperature shifts up to $130^{\circ}C$ as the concentration x increases from zero to 0.05 and shift down to $95^{\circ}C$ as further increases to 0.08. For the increase of the Curie temperature, it is suggested that it can result from the inhibition of displacement of $Ti^{4+}$ in the distorted octahedron due to well dispersed $Ba_4Ti_3P_2O_{15}$ and $Cd_5(PO_4)_3Cl$ phase.

Protonation and Stability Constants for $Co^{2+},\;Ni^{2+},\;Cu^{2+},\;and\;Zn^{2+}$ of the Open-Chain Polyamine 1-Amino-13-(2-pyridyl)-3,6,9,12-tetraaza-tridecane. Crystal Structure of Its Nickel(Ⅱ) Complex

  • 김선덕;김준광;정우식
    • Bulletin of the Korean Chemical Society
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    • v.18 no.6
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    • pp.653-656
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    • 1997
  • The new unsymmetric $N_6$ ligand 1-amino-13-(2-pyridyl)-3,6,9,12-tetraazatridecane (aptatd) containing one pyridyl group has been synthesized and characterized by EA, IR, and NMR. Its proton association constants $(log K_H^n)$ and stability constants $(log K_{ML})$ for Co(Ⅱ), Ni(Ⅱ), Cu(Ⅱ), and Zn(Ⅱ) ions were determined at 298.1 K and ionic strength 0.100 mol $dm^{-3}$ (KNO₃) in aqueous solution by potentiometry: log $K_H^1$=8.80, log $K_H^2$=8.49, log $K_H^3$=6.84, log $K_H^4$=4.17, log $K_H^5$=3.47; log $K_{ML}(Co^{2+})$=18.00, log $K_{ML}(Ni^{2+})$=21.31, log $K_{ML}(Cu^{2+})$=23.62, log $K_{ML}(Zn^{2+})$=15.60. The X-ray structure of its nickel(Ⅱ) complex [Ni(aptatd)]$(ClO_4)_2$ are reported: orthorhombic space group Pbca, a=15.715(1) Å, b=14.280(2) Å, c=19.443(2) Å, V=4363.4 (9) ų with Z=8. The geometry around nickel is a distorted octahedron with the pyridine nitrogen atom being cis to the nitrogen atom of the terminal primary amine.

Cr(III)-Tetraaza Macrocyclic Complexes Containing Auxiliary Ligands (Part IV); Synthesis and Characterization of Cr(III)-Acetylacetonato, -Malonato and -Oxalato Macrocyclic Complexes

  • Byun, Jong-Chul;Han, Chung-Hun
    • Bulletin of the Korean Chemical Society
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    • v.26 no.9
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    • pp.1395-1402
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    • 2005
  • The reaction of cis-[Cr([14]-decane)$(OH)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = acetylacetonate (acac), oxalate (ox) or malonate (mal)} leads to a new cis-[Cr([14]-decane)(acac)]$(ClO_4)_2{\cdot}(1/2)H_2O\;(1),\;cis-[Cr([14]-decane)(ox)]ClO_4{\cdot}(1/2)H_2O\;(2)\;or\;cis-[Cr([14]-decane)(mal)]ClO_4{\cdot}(1/4)H_2O\;(3)$. These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[Cr([14]-decane)(acac)]$(ClO_4)_2{\cdot}(1/2)H_2O$ reveals that central chromium(III) has a distorted octahedral coordination environment and two acetylacetonate-oxygen atoms are bonded to the chromium(III) ion in the cis positions. The angle $N_{axial}-Cr-N_{axial}$ deviates by $11^{\circ}$ from the ideal value of $180^{\circ}$ for a perfect octahedron. The bond angle O-Cr-O between the chromium(III) ion and the two acetylacetonate-oxygen atoms is close to $90^{\circ}$. The bond lengths of Cr-O between the chromium and the acetylacetonate-oxygen atoms are 1.950(3) and 1.954(2) $\AA$. They are shorter than those between chromium and nitrogen atoms of the macrocycle. The IR spectra of 1, 2 and 3 display bands at 1560 {ν (C=O)}, 1710 {${\nu}_{as}$(OCO)} and 1660 $cm^{-1}$ {${\nu}_{as}$(OCO)} attributed to the acac, ox and mal auxiliary ligands stretching vibrations, respectively.

Crystal Structure, Fluorescence Property and Theoretical Calculation of the Zn(II) Complex with o-Aminobenzoic Acid and 1,10-Phenanthroline

  • Zhang, Zhongyu;Bi, Caifeng;Fan, Yuhua;Zhang, Xia;Zhang, Nan;Yan, Xingchen;Zuo, Jian
    • Bulletin of the Korean Chemical Society
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    • v.35 no.6
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    • pp.1697-1702
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    • 2014
  • A novel complex [$Zn(phen)(o-AB)_2$] [phen: 1,10-phenanthroline o-AB: o-aminobenzoic acid] was synthesized and characterized by elemental analysis and X-ray diffraction single-crystal analysis. The crystal crystallizes in monoclinic, space group P2(1)/c with $a=7.6397(6){\AA}$, $b=16.8761(18){\AA}$, $c=17.7713(19){\AA}$, ${\alpha}=90^{\circ}$, ${\beta}=98.9570(10)^{\circ}$, ${\gamma}=90^{\circ}$, $V=2.2633(4)nm^3$, Z = 4, F(000) = 1064, S = 1.058, $Dc=1.520g{\cdot}cm^{-3}$, $R_1=0.0412$, $wR_2=0.0948$, ${\mu}=1.128mm^{-1}$. The Zn(II) is six coordinated by two nitrogen and four oxygen atoms from the 1,10-phenanthroline and o-aminobenzoic acid to furnish a distorted octahedron geometry. The complex exhibits intense fluorescence at room temperature. Theoretical studies of the title complex were carried out by density functional theory (DFT) B3LYP method. CCDC: 898291.

Cr(III)-Tetraaza Macrocyclic Complexes Containing Auxiliary Ligands (Part III); Synthesis and Characterization of Cr(III)-Isothiocyanato, -Azido and -Chloroacetato Macrocyclic Complexes

  • Byun, Jong-Chul;Han, Chung-Hun;Park, Yu-Chul
    • Bulletin of the Korean Chemical Society
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    • v.26 no.7
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    • pp.1044-1050
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    • 2005
  • The reaction of cis-[Cr([14]-decane)($OH_2)_2]^+$ ([14]-decane = rac-5,5,7,12,12,14-hexamethyl-1,4,8,11-teraazacyclotetradecane) with auxiliary ligands {$L_a$ = isothiocyanate ($NCS^-$), azide ($N3^-$) or chloroacetate(caa)} leads to a new cis-[Cr([14]-decane)($NCS)_2]ClO_4{\cdot}H_2O$ (1), cis-[Cr([14]-decane)($N_3)_2]ClO_4$ (2) or cis-[Cr([14]-decane)($caa)_2]ClO_4$ (3). These complexes have been characterized by a combination of elemental analysis, conductivity, IR and Vis spectroscopy, mass spectrometry, and X-ray crystallography. Analysis of the crystal structure of cis-[Cr([14]-decane)($NCS)_2]ClO_4{\cdot}H_2O$ reveals that central chromium(III) has a distorted octahedral coordination environment and two $NCS^-$anions are bonded to the chromium(III) ion via the Ndonor atom in the cis positions. The angle $N_{axial}-Cr-N_{axial}$ deviates by 13$^{\circ}$ from the ideal value of 180$^{\circ}$ for a perfect octahedron. The bond angle N-Cr-N between the Cr(III) ion and the two nitrogen atoms of the isothiocyanate ligands is close to 90$^{\circ}$. The bond lengths of Cr-N between the chromium and $NCS^-$groups are 1.964(5) and 2.000(5) $\AA$. They are shorter than those between chromium and nitrogen atoms of the macrocycle. The IR spectra of 1, 2 and 3 display bands at 2073, 1344 and 1684 $cm^{-1}$ attributed to the $NCS^-$, ${N_3}^-$ and caa groups stretching vibrations, respectively.

Synthesis, Crystal structure, and Magnetic Properties of Dinuclear Iron(III) Complexes with Methoxo Bridges

  • Shin, Jong-Won;Han, Jeong-Hyeong;Rowthu, Sankara Rao;Kim, Bong-Gon;Min, Kil-Sik
    • Bulletin of the Korean Chemical Society
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    • v.31 no.12
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    • pp.3617-3622
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    • 2010
  • The reaction of stoichiometric amount of $FeCl_2{\cdot}4H_2O$, (2-pyridylmethyl, 3-pyridylmethyl)amine (2,3-pyma) and sodium azide/sodium thiocyanate in methanol under aerobic conditions affords the dinuclear Fe(III) complexes, [(2,3-pyma) $(N_3)_2Fe({\mu}-OCH_3)_2Fe(N_3)_2$(2,3-pyma)]${\cdot}CH_3OH$ (1) and [(2,3-pyma)$(NCS)_2Fe({\mu}-OCH_3)_2Fe(NCS)_2$(2,3-pyma)] (2) in good yield. Two bis-methoxy-bridged diiron(III) complexes are isolated and characterized. The coordination geometries around iron(III) ions in 1 and 2 are the same tetragonally distorted octahedron. The iron(III) ions are coordinated by two nitrogens of a 2,3-pyma, two nitrogens of two azide/thiocyanate ions, and two oxygens of two methoxy groups. Both compounds are isomorphous. The structures of 1 and 2 display the C-$H{\cdots}\pi$ and/or $\pi-\pi$ stacking interactions as well as hydrogen bonding interactions, respectively. Compounds 1 and 2 show significant antiferromagnetic couplings through the bridged methoxy groups between the iron(III) ions in the temperature range from 5 to 300 K ($H=-2JS_1{\cdot}S_2$, J=-19.1 and $-13.9\;cm^{-1}$ for 1 and 2).