Two Novel Crystal Structures of 2-Mercapto-1,3,4-thiadiazole Complexes with Mercury (II) Chloride

Abstract  

Two novel complexes 1 and 2 have been simultaneously obtained by the reaction of 2-mercapto-1,3,4-thiadiazole (MTD) with mercury (II) chloride (HgCl₂) in CH₃CN, and their crystal structures are characterized by single-crystal X-ray diffraction analysis. Crystal structures show that each Hg(II) of 1 is four coordinated with two chloride anions and two exocyclic sulfur atoms of two adjacent MTDs, and each Hg(II) of 2 is three coordinated with one chloride anion, one nitrogen atom and one exocyclic sulfur atom of two adjacent MTDs, respectively. Assisting the intermolecular works such as S···S, S···Cl or Hg···S interactions, both two complexes 1 and 2 are formed 2D supramolecular architectures. The results obtained conform the MTD can exist thiol and thione forms in the solid state.     

Synthesis, Crystal Structures and Properties of Two Copper (II) Complexes with Pyridazine Derivative Ligand

Abstract  Two new complexes, [Cu(L)₂(CH₃OH)] · (ClO₄)₂ (1) and [Cu(L)₂(H₂O)] · (NO₃)₂ (2), have been synthesized and their crystal structures have been determined by X-ray analysis, where L = 3-(3,5-bimethylpyrazole-yl)-6-chloro-pyridazine]. The complex 1 crystallizes in the monoclinic, space group C2/c, and the coordination configuration of copper (II) is better described as trigonal pyramidal geometry with four N atoms from L and one O_methanol^. The coordination configuration of 2 is quite similar to that of 1 except O_water instead of O_methanol^. The intermolecular hydrogen bonds link the repeat units and extend the molecules to multinuclear structures in both compounds. The spectral properties of the title compounds have been studied and discussed. Furthermore, the antibacterial activities of the title compounds have been detected, the results indicate that the ligands and two copper(II) complexes exhibit certain fungicidal activities again several bacteria. Index Abstract  Two new complexes, [Cu(L)2(CH3OH)]·(ClO4)2 (1) and [Cu(L)2(H2O)]·(NO3)2 (2), have been synthesized and their crystal structures have been determined by X-ray analysis, where L= 3-(3,5-bimethylpyrazole-yl)-6-chloro-pyridazine. The intermolecular hydrogen bonds extend the molecules to multinuclear structures in both compounds.      

Synthesis and Crystal Structures of Dioxomolybdenum(VI) Complexes with ONS-Donor Ligands

Abstract  

Three dioxomolybdenum complexes namely dioxo(5-chlorosalicylaldehyde thiosemicarbazonato) dimethylsulfoxide molybdenum(VI) (C1), dioxo(5-chlorosalicylaldehyde 2-ethylthiosemicarbazonato) dimethylsulfoxide molybdenum(VI) (C2) and dioxo(5-chlorosalicylaldehyde N-phenylthiosemicarbazonato) dimethylsulfoxide molybdenum(VI) (C3) were prepared. The compounds all crystallize in the triclinic space group P-1 with a = 7.3184(3) ?, b = 7.5035(3) ?, c = 14.9713(6) ?, α = 85.005(2)°, β = 85.616(2)°, γ = 66.987(2)° for C1, a = 8.2339(1) ?, b = 10.1739(1) ?, c = 10.4017(1) ?, α = 78.486(1)°, β = 89.312(1)°, γ = 81.730(1)° for C2, a = 7.0591(1) ?, b = 9.5603(1) ?, c = 14.5762(2) ?, α = 76.280(1)°, β = 81.351(1)°, γ = 81.985(1)° for C3. In general, the overall geometry of these complexes can be regarded as a distorted octahedron with the tridentate thiosemicarbazonato ligands (L²⁻) bonded to the MoO₂ ²⁺ core, with the imine nitrogen, phenoxyl oxygen, sulfur atom and one of the terminal oxygen atoms of the dioxomolybdenum occupying the equatorial position. The sixth coordination site is occupied by the dimethylsulfoxide (DMSO) solvent molecules. The adjacent molecules of C1 are linked by N–H···N intermolecular hydrogen bonding, forming polymeric chains that run parallel to the bc plane. On the other hand, C2 is a discrete molecule while the molecules of C3 associate via weak N–H···O hydrogen bonding interaction to form a polymeric chain that runs along the a-axis.     

Synthesis and Crystal Structures of a Pair of Isostructural Azido-Bridged Polynuclear Schiff Base Zinc(II) Complexes

Abstract  

A pair of novel isostructural azido-bridged polynuclear zinc(II) complexes, [Zn₂(L1)₂(μ_1,1-N₃)(μ_1,3-N₃)] _n (1) and [Zn₂(L2)₂(μ_1,1-N₃)(μ_1,3-N₃)] _n (2) (HL1 = 2-bromo-4-chloro-6-[(2-isopropylaminoethylimino)methyl]phenol, HL2 = 2,4-dibromo-6-[(2-isopropylaminoethylimino)methyl]phenol), have been synthesized and structurally characterized by elemental analysis, IR spectra and single crystal X-ray diffraction. Both complexes crystallize in the orthorhombic space group Pcca. Crystal data for (1): a = 22.567(4) ?, b = 8.414(2) ?, c = 17.268(3) ?, V = 3279.0(11) ?³, Z = 8, R ₁ = 0.0441, and wR ₂ = 0.0846. Crystal data for (2): a = 22.536(4) ?, b = 8.409(2) ?, c = 17.531(3) ?, V = 3322.2(11) ?³, Z = 8, R ₁ = 0.0538, and wR ₂ = 0.0906. X-ray structure determination revealed that each zinc(II) atom in the complexes is in a trigonal–bipyramidal coordination, with one imine N atom of a Schiff base ligand and two N atoms from two bridging azide ligands defining the basal plane, and one phenolate O and one amine N atoms of the Schiff base ligand occupying the two axial positions.     

Synthesis,Properties, and Crystal Structures of Copper(II) Di-(2-picolyl)amine Complexes Containing Inorganic Salts

Abstract These complexes have been characterized by X-ray crystallography, spectroscopic, and cyclic voltammetry. In 1, the copper(II) ion has a distorted square-pyramidal geometry with three nitrogen atoms of the dpa ligand and two oxygen atoms of the nitrate anions. The crystal structure of 2 shows that the copper(II) ions are bridged by tp anion to form a dinuclear complex, in which each copper(II) ion exhibits a distorted square-pyramid with three nitrogen atoms of the dpa ligand, water molecule, and the oxygen atom of the bridging tp ligand. Cyclic voltammetric data indicate that 1 undergoes irreversible one-electron oxidation to the Cu^III and reversible one-electron reduction to the Cu^I, while 2 gives one reversible oxidation and two reversible and irreversible reduced processes. The electronic spectra and redox potentials of the complexes are influenced significantly by the anionic ligands. Graphical Abstract The reaction of [Cu(dpa)Cl₂] with K(NO₃)₂ and Na₂tp yields mononuclear and dinuclear copper(II) complexes [Cu(dpa)(NO₃)₂] (1) and [Cu₂(dpa)₂(H₂O)₂(μ-tp)](tp)·6H₂O (2) (dpa = di-(2-picolyl)amine, tp = terephthalate).      

Synthesis,Crystal Structures and Fluorescence Properties of Ni (II) and Cu (II) Complexes with 1-(Furan-2-ylmethylene)-4-phenylthiosemicarbazone

Abstract  

Two coordination complexes, NiL ₂ and CuL ₂ {L = bis[1-(furan-2-ylmethylene)-4-phenylthiosemicarbazone]}, were synthesized and determined by X-ray crystallography. Both crystallize in the Orthorhombic system, space group Pbcn, with lattice parameters: a = 11.935 (2) Å, b = 15.314(3) Å, c = 12.952(3) Å and Z = 4 for Ni (II); a = 20.850(4) Å, b = 15.049(3) Å, c = 7.5633(5) Å and Z = 4 for Cu (II). In both complexes, the central metal atom is coordinated in a distorted square-planar with two ligands through two S and N atoms, respectively. The EA, UV, IR and TG-DTG were studied and the possible structures of the complexes were speculated. Moreover, the fluorescence of the complexes were studied. The results reveal that copper complex can emit purple fluorescence in solvents.     

Syntheses,Crystal Structures and Fluorescence Properties of Zn(II) Complexes with Pyrazolone Derivatives

Abstract   N-(1,3-Diphenyl-4-benzal-5-pyrazolone)-salicylidene hydrazone(H₂L ¹ ) and its zinc complex Zn(HL ¹ )₂ · 2CH₃OH (1) have been synthesized and characterized by elemental analyses, IR spectra, thermal analyses and single-crystal X-ray diffraction studies. The X-ray diffraction analyses of the complex Zn(HL ¹ )₂ · 2CH₃OH (1) and the known compound Zn₄(L ² )₄ (2) (H₂L ²  = N-(1,3-diphenyl-4-phenylethylene-5-pyrazolone)-salicylidene hydrazone) show that different acyl groups in position 4 of pyrazolones may lead to the different coordination mode of the ligands and distinctive structures of the same central metal Zn(II) complexes, of which 1 is a mononuclear complex while 2 is a tetranuclear complex. Meanwhile, two Zn(II) complexes have different thermal stabilities and fluorescence properties. Graphical Abstract        

异构体复晶-席夫碱锌配合物的合成、晶体结构及表征

以2-乙酰吡啶、高氯酸锌和2-氨基乙基-二(3-氨基丙基)胺为原料在甲醇介质中反应制备全氮配位的异构体复晶-席夫碱锌配合物,用元素分析、红外光谱、核磁共振氢谱和热重分析对其进行了表征,用X射线单晶衍射仪测定其晶体结构,结果表明该异构体复晶-席夫碱锌配合物属于单斜晶系,P2(1)/c空间群.晶胞参数分别为a=1.8517(6) nm,b=1.5341(5) nm,c= 1.6061(5) nm,α=γ=90 °,β=90.743(6) °,V=4.562(2) nm3 ;Dc=1.577 g/cm3;Z= 4, F(000)=2240; μ=1.361 mm-1.     

X-Ray Crystal Structures of Two Monopentamethylcyclopentadienylhafnium(IV) Complexes

Crystallography Reports - The crystal structures of two monopentamethylcyclopentadienylhafnium(IV) derivatives have been determined by X-ray diffraction analysis. The [Hf(η5-C5Me5)Cl3] complex...     

1,2,3-三唑羧酸铜(Ⅱ)配合物的合成、晶体结构与性质

通过水热的方法制备了两个新的1,2,3-三唑羧酸铜配合物:[Cu(L1)2· 2H2O](1)和[Cu(L2)2]n(2)(HL1=4-苯基-1,2,3-三唑-1-乙酸,HL2=4-苯基-1,2,3-三唑-2-乙酸),并利用红外光谱、质谱(MS)、核磁共振氢谱(1 H NMR)、元素分析、X-射线单晶衍射、X-射线粉末衍射和热重分析进行了表征.晶体结构表明:配合物1中,每一个单核分子通过分子间氢键作用形成二维层状结构.配合物2中,铜原子通过与羧基上的氧原子采用顺-反双齿桥联,形成了二维的网状结构,进一步通过每层网状结构间的π-π堆积作用形成三维超分子结构.磁性测试结果表明配合物2在低温下表现为铁磁性相互作用.     

Synthesis,Crystal Structure and Physicochemical Characterization of Two Ni(II)-Famotidine Metal Complexes

The coordination ability of the antisecretor agent Famotidine (FMT) was explored using Ni(II) as central ion. [NiFMT_H-2] and [Ni(FMT)₂]Cl₂ were obtained by the solvent evaporation method from the corresponding starting solutions at pH 8 and 4, respectively; the crystal structure was elucidated by single crystal X-ray diffraction in both cases.[NiFMT_H-2] resulted in a distorted square-planar geometry, where FMT acts as a tetradentate dianionic ligand through nitrogen atoms belonging to the guanidine group, the thiazolic ring and the side chain, and a sulfur atom from the thioether moiety. [Ni(FMT)₂]Cl₂ exhibits an octahedral environment composed by two FMT molecules that coordinate by nitrogen atoms deriving from guanidine and thiazole ring moieties, and the thioether sulfur atom. The physicochemical characterization was completed by means of FTIR and UV–Vis spectroscopies, and thermal analysis. Solubility measurements were performed and the results could be satisfactorily correlated with the solvation Gibbs free energy (ΔG_solv) values in aqueous solution obtained using the SDM model by DFT calculations.

Graphic Abstract

Ni(II) and famotidine form an octahedral complex at pH 4 where famotidine acts as a tridentate neutral ligand. In basic medium, it behaves as a tetradentate dianion, resulting in a quasi-planar complex. Spectroscopic and thermal data are consistent with single crystal X-ray diffraction structural elucidation. The relative stabilities were assessed by theoretical studies.

     

Synthesis and Crystal Structure of Copper(II)-Hexafluoro-Acetylacetonate Complexes with Pyridyl-Substituted Nitronyl and Imino-Nitroxide Radicals

Abstract  

A one-dimensional chain compound was formed by copper (II) hexafluoroacetylacetonate (hfac) and nitroxide radical 2-(4-pyridyl)-4,4,5,5-tetramethyl-imidazoline-1-oxyl-oxide (NITpPy). The product was structurally characterized by single crystal X-ray diffraction. [Cu₂(hfac)₄NITpPy] _n crystallizes in the monoclinic C₂/c space group with a = 19.70(2), b = 16.834(19), c = 15.274(18) ?, β = 119.073, V = 4427(9) ?³, Z = 4, R = 0.0699 wR ₂ (all data) = 0.1752. In the compound, two different Cu(hfac)₂ units are bridged by NITpPy. The nitrogen atom of pyridine ring is coordinated with Cu(II) ion to afford a three-spin complex. Cu(II) ions of Cu(hfac)₂ and the oxygen atoms of nitronyl nitroxide formed weak coordination bonds with the bond length 2.495(8) ?.