Synthesis and Characterization of Chiral Mercury(II) and Cadmium(II) Complexes with 3,3'-Bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl

Two homochiral mercury （1） and cadmium （2） complexes derived from chiral twisted biphenyl pyridine ligand （3,3＇-bipyridine-5,5＇,6,6＇-tetramethyl-2,2＇-dimethoxy-1,1＇-biphenyl） have been synthesized and characterized by IR, microanalysis, TGA, UV-Vis, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 2. For 1, a = 14.2038（16）, b = 14.3630（17）, c = 7.0257（8）, V = 1433.3（3）3, Mr = 878.91, Dc = 2.037 g/cm3, μ = 7.549 mm-1, F（000） = 824, the final GOF = 1.017, R = 0.0296 and wR = 0.0645 for 2925 observed reflections with I 2σ（I）. For 2, a = 14.212（3）, b = 14.392（3）, c = 7.0498（14）, V = 1442.0（5）3, Mr = 790.72, Dc = 1.821 g/cm3, μ = 2.924 mm–1, F（000） = 760, the final GOF = 1.075, R = 0.0340 and wR = 0.0834 for 3144 observed reflections with I 2σ（I）. The crystal structures of 1 and 2 are isostructural and each adopts a two-dimensional supramolecular network which contains the C–H···π interactions.

Syntheses,Crystal Structures,DFT Calculation and Optical Properties of a Schiff Base and Its Dinuclear Mercury(Ⅱ)Complex

A pyridine-contained Schiff base ligand L（L =（pyridine-2-vinyl）hydrazine） has been synthesized and fully characterized. By self-assembly of the ligand with HgI2, a binuclear complex Hg2I4L（C） was obtained. The structures of L and C were analyzed through single-crystal X-ray diffraction. L crystallizes in monoclinic, space group P21/n with a=11.286（5）, b=3.981（5）, c=23.865（5） , β=100.043（5）°, V=1056（1） 3, Z=4, Dc=1.323 g/m3, F（000）=440, Μr=210.24, μ=0.084 mm（-1）, the final R=0.0928 and w R=0.2867 for 6955 observed reflections with I ＆gt; 2（I）. The complex is of monoclinic system, space group P21/n with a=8.706（5）, b=17.468（5）, c=14.675（5） , β=93.922（5）°, V=2227（2） 3, Z=4, Dc=3.338 g/m3, F（000）=1928, Μr=1119.02, μ=19.321 mm（-1）, the final R=0.0366 and w R=0.1276 for 3920 observed reflections with I ＆gt; 2（I）. The structural analysis revealed that the molecule of L possesses a well planar structure. However, in the complex, the coordinated ligand distorts greatly. The absorption spectra of L and the complex in ethanol were experimentally and theoretically studied. The result indicates that the complex exhibits different absorption spectrum compared with the free ligand.

Studies on the Crystal Structure and Photoluminescence of a Mercury(Ⅱ)Complex Based on a Novel Pyridine Ligand

A novel mercury（H） complex HgL2Br2 was prepared from HgBr2 and the organic ligand 2-（N-methyl-N-（4-（（E）-2-（pyridine-4-yl）vinyl）phenyl）amino）ethanol （L）. The ligand was synthesized and then characterized by FT-IR spectroscopy, tH NMR, mass spectrum and elemental analysis, while the single-crystal diffraction data of the complex were collected on a Siemens Smart CCD diffractometer. The complex crystallizes in triclinic space group PI with a = 5.367（5）, b = 12.466（5）, c = 23.945（5） A, α = 90.812（5）, β = 96.318（4）, γ = 96.093（5）°, Z = 2, Dc = 1.817 g.cm3,μ = 7.395 mm^-1, S = 0.825, and the final R= 0.0396. The Hg（Ⅱ） ion in the distorted tetrahedral mercury（Ⅱ） complex C32H36HgBr2N4O2 is coordinated by two N atoms from the two ligands together with two bromide ions. Solid-state emission of the ligand and its complex has been investigated at room temperature.

Structural Studies and Photoluminescence of a Novel Mercury(Ⅱ) Complex Based on a Tris[4-(1-pyrazolyl)-phenyl]amine

A novel iodine-bridged mercury（Ⅱ） complex [Hg（L）（μ-I）（I）]2 was isolated by a reaction between HgI2 and the organic ligand tris[4-（1-pyrazolyl）phenyl]amine L, and the complex and ligand were both characterized by FT-IR spectroscopy, ^1H NMR and elemental analysis. The complex crystallizes in monoclinic space group P21/c with a = 9.579（5）, b = 27.331 （5）, c = 11.268（5） А, β= 105.624（5）°, Z = 2, Dc = 2.099 g·cm^-3 and μ= 7.620 mm^-1. The title complex C54H42Hg2I4N14 is a diplex bridged dinuclear complex consisting of two Hg（Ⅱ） ions, two ligands, two bridging I-anions, and two terminal I-anions. Universal hydrogen bonds in the complex with the partners of neighboring molecule have generated a supramolecular arrangement. Solid-state emission of the ligand and its complex have been investigated at room temperature.

Two-dimensional Supramolecular Structure of a Mercury(Ⅱ) Iodide Complex with Organosulfide

A mercury（Ⅱ） iodide complex with organosulfide [Hg（pymt）（pymtH）I] 1 （pymt = the anion of pyrimidine-2-thiolate） has been synthesized by slow evaporation of the solution at room temperature and structurally characterized by single-crystal X-ray diffraction. Basic ideas and data collected are given. X-ray diffraction analysis reveals that complex 1 is mononuclear. Crystallographic data： C8H7HgIN4S2, Mr = 550.79, monoclinic system, space group P21/c, a = 11.218（4）, b = 9.551（3）, c = 15.877（4） A^°, β = 129.697（15）°, V = 1308.9（7） A^°^3, Z = 4, Mr = 550.79, Dc = 2.795 g/cm^3, F（000） = 995, μ（MoKa） = 14.415 mm^-1, 2（MoKa） = 0.71073 A^°, T= 293（2） K, 2θmax = 54.9°, GOOF= 1.053, the final R = 0.0310 and wR = 0.0742 for 2547 observed reflections with I 〉 2σ（I） （refinement on F^2）. Complex 1 is connected through hydrogen bonds to give a one-dimensional supramolecular chain structure. Furthermore, π-π interactions are also found between the pyrimidine rings with the center-to-center distances of 3.439（4） and 3.603（4） A^°, so complex 1 expands the chains into a two-dimensional network.

Study on the Mercury （11） Complex of 4,5-benzol,2-dithiole-3-thione by IR, Theoricaly and X-Ray

A mercury （II） complex with 4.5-benzo-1.2-dithiol-3-thione （C7H4S3） （1）, [Hg2I4（C7H4S3）2] （2） was synthesized. The structure of the obtained complex （2） was characterized by crystallography, Infrared Spectroscopy （IR） analysis and theoretical study. The complex （2） has a dimeric structure, where each mercury atom takes a tetrahedral geometry and is coordinated by two bridging chloride, one terminal chloride and one thiocarbonyl sulfur atom （C=S） of the ligand.

Two Novel Mercury(Ⅱ) and Copper(Ⅱ) Complexes Based on(5-Chloro-quinolin-8-yloxy)acetic Acid

Two novel mononuclear complexes with 5-chloro-8-（methoxycarbonylmethoxy）quinoline ligand（L）, namely, HgLBr2 1 and CuL2Cl2 2, have been prepared by solvothermal reaction of（5-chloro-quinolin-8-yloxy）acetic acid with HgBr2 and CuCl2, respectively. Their structures were characterized by IR, elemental analysis, UV-Vis-NIR spectra, TG and single-crystal X-ray diffraction analysis. Interestingly,（5-chloro-quinolin-8-yloxy）acetic acid is changed as 5-chloro-8-（methoxycarbonylmethoxy）quinoline ligand（L） in complexes 1 and 2. Crystal data for 1： C12H10Br2 Cl Hg NO3, Mr = 612.07, triclinic, space group P1 with a = 8.5983（7）, b = 9.7726（6）, c = 10.1549（6） A, α = 66.355（6）, β = 77.067（8）, γ = 78.803（8）°, V = 756.6（9）A^3, Z = 2, Dc = 2.687 g/cm^3, F（000） = 560, μ = 15.633 mm^-1, R = 0.0351 and w R = 0.0504. Crystal data for 2： C24H20Cl4 Cu N2O6, Mr = 637.76, triclinic, space group P1 with a = 10.5324（9）, b = 11.2377（16）, c = 12.0143（12） ？, α = 83.413（11）, β = 64.475（9）, γ = 83.144（11）°, V = 1270.9（2） ？3, Z = 2, Dc = 1.667 g/cm3, F（000） = 646, μ = 1.324 mm-1, R = 0.0408 and wR = 0.0922. In 1, the HgII centre is a distorted trigonal planar geometry comprised of two Br atoms and one quinoline N atom of L. Intermolecular π-π, C–H…π stacking interactions and intermolecular C–H…Br hydrogen bonds are observed in the molecular packing of 1. In complex 2, each CuII center has a distorted octahedral geometry comprised of two chloride ions, two quinoline N atoms and two O atoms of two L ligands. Intermolecular C–H…Cl hydrogen bonds exist in the molecular packing of 2. The fluorescence emission peak of complexes 1 and 2 appears near 406 and 410 nm, respectively. Optical diffuse-reflection spectral results suggest complex 1 has the property of semiconductor.

Synthesis and Crystal Structure of Mercury BridgedBiferrocene Trinuclear Complex Hg(FcL)_2,Bis(S-methyl-N-(1-ferrocenyl-1-methyl)methylenedithiocarbazate)mercury(Ⅱ)

The title complex, mercury bridged biferrocene trinuclear complex Hg(FcL)2. Bis (S-methyl-N- (1-ferrocenyl-1-methyl) methylenedithiocarbazate) mercury,Crystallizes in space group Pbca with a =19. 510 (4), b=19. 921 (5), c=15. 581 (3)A. V=6095(3) A, Z=8,M.=863. 12, Dc=1.881 g/cm3; u=19. 24 cm-1 and F(000) = 3376. The final refinement of 2455 observed reflections is converged with R= 0. 043 and Rw=0.047. X-ray crystal structure analysis revealed that the coordinationgeometry of Hg atom is a distorted tetrahedron with two Hg-N bonds and two Hg- S bonds. The Schiff-base ligand loses a proton from its tautomeric thiol form and is cryordianted to the Hg aotm uia the mercapto sulphur and the β-nitrogen atoms.

Synthesis and Structural Characterization of a New 1D Polymeric Energetic Complex [Hg(DAT)Cl_2]_n (DAT = 1,5-Diaminotetrazole)

A new energetic complex [Hg（DAT）Cl2]n was synthesized by the reaction of 1,5-diaminotetrazole with mercury bichloride and characterized by elemental analysis, IR spectroscopy and X-ray single-crystal diffraction. The crystal belongs to the monoclinic system with P21/c space group, and a = 4.0342（3）, b = 17.7999（12）, c = 10.0127（7） , β = 91.558（1）°, V = 718.73（9） 3, Z = 4, CH4Cl2HgN6, Mr = 371.59, Dc = 3.434 g·cm-3, F（000） = 664, S = 1.037, the final R = 0.0223 and wR = 0.0642 for 1646 observed reflections with Ⅰ 〉 2σ（Ⅰ）. The central Hg is coordinated by one N atom from 1,5-diaminotetrazole and one mono-dentate terminal chloride and two bi-dentate bridging chloride ligands. Adjacent Hg cations were connected by the bi-dentate Cl to form a 1D zigzag supramolecular chain along the a-axis.

Synthesis of Quinoxalinophenazine Derivatives and Reaction of 3,12-Dimethylbenzo[a]quinoxalino-[2,3-c]phenazine with Mercury(Ⅱ) Bromide: Spectral and Structural Characterization

A new series of quinoxalinophenazine derivatives were synthesized in good yields by the reaction of 2,3-dibromonaphthalene-1,4-dione with different aryl-1,2-diamines in DMF as solvent at 120-130℃ or under reflux conditions. 3,12-dimethylbenzo[a]quinoxalino[2,3-c] phenazine with bidentate character reacts with mercury（II） bromide to give suitable crystals. All products were confirmed by IR, ^1H and ^13C NMR, and the metal complex by single-crystal X-ray method. The crystal（C24H16Br2HgN4, Mr = 720.82） belongs to the triclinic system, space group P1 with a = 10.186（6）, b = 10.421（6）, c = 11.470（7） A, α = 98.670（7）, β = 95.069（7）, γ = 109.831（7）°, V = 1119.4（12） A3, Z = 2, Dc = 2.139 Mg/m^3, μ = 10.46 mm^-1, F（000） = 676, R = 0.043 and wR = 0.115 for 3982 observed reflections with I 〉 2σ（I）.

Analytical, Spectral, Thermal and Molecular Modeling Studies of Hg2+-2,3-Butanedionemonoxime Girard’s T Hydrazone Complex and Its Application

The coordination behavior of 2,3-butanedionemonoxime Girard’s T hydrazone (L1) towards Hg2+ ion has been investigated. The structure of Hg2+ complex, [Hg(L1)Cl]Cl·5H2O, is elucidated using elemental analyses, spectral (IR, UV-visible, 1H-NMR and mass) and TGA measurements. IR spectrum suggests that L1 behaves in a bidentate manner through the azomethine groups. The molecular modeling of L1 and its Hg2+ complex has been investigated. The bond lengths, bond angles, HOMO and LUMO have been calculated. The thermal behavior and kinetic parameters are determined using Coats-Redfern method. The use of L1 for preconcentration and separation via flotation of Hg2+ complex and determination using cold vapor atomic spectrometry (CVAAS) is described. The effects on the percentage of recovered Hg2+ by pH of sample solutions, oleic acid (HOL) concentration, Hg2+ and L1 concentrations are studied in details. The method is applied for the determination of the total Hg2+ (mg·mL-1) in natural water samples.

One-dimensional Zigzag Chain Composed of HgI_2 Unit and 2,5-Bis(4-pyridyl)-1,3,4-thiadiazole:[HgI_2(C_(12)H_8N_4S)]

The title compound, [HgI2（C12H8N4S）], has been synthesized and characterized by single-crystal X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/n with a = 14.086（2）, b = 6.0365（6）, c = 20.286（2）°A,β= 108.818（5）°, V = 1632.7（3）°A^3, Mr = 694.67, Z = 4, D, = 2.826 g/cm^3,μ= 13.331 mm^-1, F（000） = 1240, S = 1.108, the final R = 0.0438 and wR = 0.0934 for 3085 observed reflections （I〉 2σ（I））. The Hg（Ⅱ） atom is coordinated by two 2,5-bis（4-pyridyl）-1,3,4-thiadiazole （L） molecules and two iodine anions in a distorted tetrahedral coordination geometry. Mercury atoms are linked by the organic ligands to form a one-dimensional zigzag chain. It is noteworthy that such 1D zigzag chains are extended into a two-dimensional double layer framework through I…I interactions

Synthesis and Crystal Structure of (Bu_4N)_2Hg(i-mnt)_2

The synthesis and the crystal structure of the title compound (Bu4N)(2)Hg(S2C=C(CN)(2))(2) 1 is reported herein. The crystal is attributed to trielinic system and space group P-1, fw=965.88. The crystal lattice parameters are a=9.45(1), b=15.827(2), c=17.619(2)Angstrom, alpha =108.12(2), beta =99.54(2), gamma =97.60(2)degrees, V=2421.9(8)Angstrom, mu (MoKalpha)=3.390mm(-1), Z=2, D-c=1.324g.cm(-3), F(000)=996, R=0.054, wR=0.058.