• Bulletin of the Korean Chemical Society
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• 제28권11호
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• pp.2045-2050
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• 2007

The reactions of mercury(II) chloride with O3S2-donor macrocyclic ligands with (L1) and without (L2) dibenzosubunit afforded respective exo- (1) and endo-coordinated (2) complexes depending on the ring rigidity of the ligands. From the X-ray crystal structures and comparative NMR studies for the complexes 1 and 2, it is confirmed that the resulting species with different coordination modes exist not only in solid state but also in solution state.

• Bulletin of the Korean Chemical Society
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• 제25권6호
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• pp.823-828
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• 2004

The crystal structures of sparteinium tetrachlorocuprate monohydrate $[(C_{15}H_{28}N_2)CuCl_4{\cdot}H_2O]$, 1 and sparteinium tetrabromocuprate monohydrate $[(C_{15}H_{28}N_2)CBr_4{\cdot}H_2O]$, 2, were determined. The structures of 1 [orthorhombic, $P2_12_12_1$, a = 8.3080(10) ${\AA}$, b = 14.6797(19) ${\AA}$ and c = 16.4731(17) ${\AA}$], and 2 [orthorhombic, $P2_12_12_1$, a = 8.4769(7) ${\AA}$, b = 15.166(3) ${\AA}$ and c = 16.679(3) ${\AA}$], are composed of a doubly protonated sparteinium cation, $[C_{15}H_{28}N_2]^{2+}$, a discrete $CuX_4^{2-}$ anion $(X=Cl^-\;or\;Br^-)$, and one water molecule. These monomeric compounds are stabilized through various types of hydrogen bonding interaction in their packing structures. Crystal 2 exhibits weak anti-ferromagnetism (J = -3.24 $cm^{-1}$) as opposed to the magnetically isolated paramagnetism observed for 1. The results of comparative magneto-structural investigations of 1 and 2 suggest that the pathway for the weak anti-ferromagnetic super-exchange in 2 might be through a Cu-Br${\cdots}$Br-Cu contact.

• Bulletin of the Korean Chemical Society
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• 제31권12호
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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).