Syntheses,crystal structures and characterization of divalent transition metal sulfonate complexes with O-phenanthroline

Two new complexes, [Zn(phen)₂(H₂O)₂]2L·H₂O (1) and [Cu(phen)(L)(H₂O)₂]L·3H₂O (2), where HL?= 4-aminobenzenesulfonic acid and phen = o-phenanthroline, have been synthesized and their crystal structures determined by X-ray diffraction. In the complexes the Cu(II) and Zn(II) atoms revealed two different coordination environments. Complex 1 consists of a cation [Zn(phen)₂(H₂O)₂]²⁺, in which Zn(II) is six-coordinated by four nitrogen atoms from two o-phenanthroline molecules and by two water molecules. Complex 2 has two crystallographically unique Cu(II) ions, where Cu(II) ion is five-coordinate with two nitrogen atoms of o-phenanthroline, two water molecules and one sulfonate oxygen atom. The electrochemical behavior and FT-IR of the two compounds have also been studied in detail.     

过渡金属-4, 4'-联吡啶配合物的合成及其晶体结构

由过渡金属与4,4'-联吡啶反应,得到两种新型配合物[Zn(4,4'-bpy)~2(H~2O)~2](pic)~2·(4,4'-bpy)·(H~2O)(1)与[Cu(4,4'-bpy)(pic)~2](2)(4,4'bpy:4,4'-联吡啶,pic^-:苦味酸根),进行了元素分析、红外光谱、X射线衍射等表征。X射线衍射结果表明,晶体1属单斜晶系,空间群为C~c,晶胞参数为：a=2.2716(2)nm,b=1.6191(3)nm,c=1.6166(2)nm,β=131.085(7)°,V=4.481(2)nm^3,Z=4;该配合物由4,4'-联吡啶与金属配位形成多孔的二维网,二维网再由未配位的4,4'-联吡啶通过氢键作用沿a方向堆积得三维网状结构,未配位的4,4'-联吡啶、水、苦味酸根离子就被包含在这种网络之中,展示出一定的包合现象,晶体2属三斜晶系,空间群为P1,晶胞参数为：a=0.6100(2)nm,b=1.0186(3)nm,c=1.1046(2)nm,α=107.230(10)°,β=101.992(2)°,γ=97.87(7)°,V=0.6266(3)nm^3,Z=1。在该配合物中,4,4'-联吡啶分子、苦味酸根离子均与铜离子配位,形成一维链状结构。     

Syntheses,crystal structures,and electrochemistry of novel Fe2SN and FeSN carbonyl complexes with pendant bases

Reactions of Fe₂(CO)₉ with thioacylhydrazones ArCH=NNHCSPh in THF afford Fe₂(CO)₆(μ-κ²S:κ²N-PhC(S)=NNCHArCHArN(CHAr)N=CSPh) (1, Ar?=?C₆H₅; 3, Ar?=?4-CH₃C₆H₄) and Fe(CO)₃(κ²S:N-PhC(=S)NHNCHArCHArN(CHAr)N=CSPh) (2, Ar?=?C₆H₅; 4, Ar?=?4-CH₃C₆H₄). They have been characterized by elemental analyses, IR, ¹H NMR, and ¹³C NMR and structurally determined by X-ray crystallography. Electrochemical studies reveal that when using HOAc as a proton source, they exhibit high catalytic H₂-production.     

Syntheses,crystal structures and thermoanalyses of alkaline earth metal complexes derived from dinitropyridone

Six new alkaline-earth metal compounds derived from dinitropyridone ligands (3,5-dinitropyrid-2-one, 2HDNP; 3,5-dinitropyrid-4-one, 4HDNP and 3,5-dinitropyrid-4-one-N-hydroxide, 4HDNPO) were synthesized and characterized by elemental analysis, FT-IR and partly by powder XRD, TG-DSC and X-ray single-crystal diffraction analysis. The structural determination revealed that one molecule of both magnesium salts (Mg(2DNP)₂ ·?8H₂O, (1), and Mg(4DNP)₂ ·?6H₂O (4)) comprise one cation [Mg(H₂O)₆]²⁺ and two anions displaying centro-symmetry with the Mg atom located at the center. Two anions (and crystalline water molecules) are joined by hydrogen bonds. The barium salt Ba(4DNP)₂ ·?4H₂O (5), is a centro-symmetric dimer with each Ba(II) being coordinated by one monodentate ligand anion, two bidentate ligand anions (different coordination pattern) and five water molecules. Another barium salt, Ba(4DNPO)₂ ·?6H₂O (6), is a coordination polymer, the ten-coordinate (BaO₁₀) barium environment comprising four water molecules, a pair of 4DNPOs via the pyridine-N-oxide oxygen, and one 4DNPOs from an adjacent metal atom offering chelating nitro group oxygen, bridging adjacent bariums. Abundant intermolecular hydrogen bonds link the molecules of each complex into multi-dimensional chains. The X-ray powder diffraction analysis confirmed the phase homogeneity of the polycrystalline samples. The TG-DSC results revealed that Mg(2DNP)₂ ·?8H₂O and Ba(4DNP)₂ ·?6H₂O each has three main weight-loss stages. The first step is the loss of all water molecules and the last step is the loss of the nitro groups and/or decomposition of the pyridine rings with the release of heat.     

Syntheses,crystal structures,and electrochemical properties of transition metal complexes with new tetrathiafulvalene-derivatized acetylacetonate ligands

Two new tetrathiafulvalene (TTF) derivatives of acetylacetone, namely, 3-[{6,7-benzo-2-(methylthio)-TTF-3-yl}-thio]-2,4-pentanedione (L₁) and 3-[{6,7-(ethylenedithio)-2-(methylthio)-TTF-3-yl}-thio]-2,4-pentanedione (L₂), have been synthesized. Four transition metal(II) complexes of these ligands, of general formulae [Zn(L₁)₂(THF)₂] and [M(L₂)₂(THF)₂] (M = Zn, Mn, and Ni), have been prepared and structurally characterized. The redox properties of both the ligands and their complexes were investigated by cyclic voltammetry. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users. Peng Zheng and Yun-Jun Guo contributed equally to this work.     

Syntheses and crystal structures of a series of new divalent metal phosphonates with imino-bis(methylphosphonic acid)

Hydrothermal reactions of divalent transition metal salts with imino-bis(methylphosphonic acid), NH(CH₂PO₃H₂)₂ (H₄L) afforded three new metal phosphonates, namely, Cu[NH(CH₂PO₃H)₂] 1, {Co[NH₂(CH₂PO₃H)(CH₂PO₃)](H₂O)₂}·H₂O 2 and Mn[NH₂(CH₂PO₃H)(CH₂PO₃)](H₂O) 3. When HO₂C(CH₂)₃N(CH₂PO₃H₂)₂ was used as the phosphonate ligand and 4,4′-bipy as the second metal linker, {Cu₄[NH(CH₂PO₃)₂]₂(4,4′-bipy)(H₂O)₄}·9H₂O 4 with a pillared layered architecture was obtained. The NH(CH₂PO₃)₂ anion resulted from the cleavage of the HO₂C(CH₂)₃-group during the reaction. Although compounds 1-3 have a same M/L ratio (1:1), they exhibit totally different structures.Compound 1 has a linear chain structure, in which each pair of square-pyramidal coordinated copper(II) ions are bridged by two phosphonate oxygen atoms to form a Cu₂O₂ dimeric unit, and such dimeric units are further interconnected via phosphonate groups to form a [010] chain. Compound 2 has a layered architecture built from CoO₆ octahedra bridged by phosphonate ligands. In compound 3, the interconnection of the manganese(II) ions by bridging imino-diphosphonate ligands leads to a 3D network. Compound 4 has a pillar-layered structure, the layers composed of Cu(II) ions bridged by aminodiphosphonate ligands are interconnected by 4,4′-bipy ligands to form channels along c-axis. Several factors that affect the structures of the metal phosphonates formed have also been discussed. Compounds 2 and 3 show predominant antiferromagnetic interactions between magnetic centers.     

Syntheses and crystal structures of group 6 metal complexes containing allyl and cyanotrihydroborate groups

Compounds M(η³-C₃H₅)(CO)₂(NCCH₃)₂(NCBH₃) and [N(CH₃)₄]₂[M(η³-C₃H₅)(CO)₂(NCBH₃)₃] (M = Mo, W) were prepared and structurally characterized. In the solid state, the allyl group orients its open face to the two carbonyl groups producing an endo form in the above compounds. In solution, an exo form coexists with an endo form in compound Mo(η³-C₃H₅)(CO)₂(NCCH₃)₂(NCBH₃). The cyanotrihydroborate ligand bonds to the metal through a nitrogen atom. Both of the IR and the 11B NMR spectroscopic data suggest the negative charge of the cyanotrihydroborate ligand on the complex is almost localized on the BH₃ and this negative charge only has small effect on the metal-nitrogen interaction.     

Fullerene complexes with divalent metal dithiocarbamates: structures,magnetic properties,and photoconductivity

A series of complexes of fullerenes C₆₀ and C₇₀ with metal dithiocarbamates {M^II(R₂dtc)₂}·C_m (m = 60 or 70) and metal dithiocarbamates coordinated to nitrogen-containing ligands (L), {M^II(R₂dtc)₂)_x·L}·C₆₀ (x = 1 or 2), where M = Cu, Zn, Cd, Hg, Mn, or Fe, R = Me, Et, Prⁿ, Prⁱ, or Buⁿ, L is 1,4-diazabicyclo[2.2.2]octane (DABCO), N,N′-dimethylpiperazine, or hexamethylenetetramine, were synthesized. The shape of dithiocarbamate molecules is sterically compatible with the spherical shape of C₆₀, resulting in an efficient interaction between their π systems. The resulting compounds are characterized by a layered or three-dimensional packing of the fullerene molecules. In the C₆₀ complexes, iron(II) and manganese(II) dithiocarbamates exist in the high-spin states (S = 2 and 5/2). The magnetic susceptibility of {M^II(Et₂dtc)₂}₂·C_m (M = Fe or Mn, m = 60 or 70) in the temperature range of 200–300 K is described by the Curie-Weiss law with Θ = −250 and −96 K and with maxima at 110 and 46 K, respectively, which is indicative of a strong antiferromagnetic spin coupling between M^II. The Weiss constants for the [{M^II(Et₂dtc)₂}₂·DABCO]·C₆₀·(DABCO)₂ complexes (M = Fe or Mn) are 1.7 and 0.3 K, respectively. The magnetic moments of the complexes containing Fe and Mn dithiocarbamates slightly increase at temperatures below 50 and 35 K, respectively, which is evidence of the ferromagnetic spin coupling between M^II in {M^II(Et₂dtc)₂}₂·DABCO. Single crystals of the complexes exhibit low dark conductivity (10⁻¹⁰–10⁻¹¹ S cm⁻¹). The visible light irradiation of these crystals leads to an increase in the photocurrent by two–three orders of magnitude. The photogeneration of free charge carriers in the complexes occurs both due to the photoexcitation of metal dithiocarbamate (Cu^II(Et₂dtc)₂) and through the charge transfer from metal dithiocarbamate (M^II(Et₂dtc)₂, M = Zn or Cd) to C₆₀. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2072–2087, November, 2007.     

Syntheses,crystal structures,and properties of four transition metal complexes based on 5-nitro-8-hydroxyquinoline

Four new complexes, [M(C₉H₅N₂O₃)₂(H₂O)₂]·CH₃OH (M?=?Zn(II), Cd(II) and Mn(II)) (1–3) and [Cu(C₉H₅N₂O₃)₂] (4), have been synthesized by reactions of 5-nitro-quinoline-8-yl acetate (NQA) and corresponding metal salts at room temperature and characterized by elemental analysis, IR, thermal gravimetric analysis (TGA), fluorescence measurement and single crystal X-ray diffraction. 1–3 are mononuclear, further extended to 2-D layers by hydrogen bonds. For 4, Cu²⁺ is coordinated by two N atoms and two O atoms from two NQ ligands. TGA indicates that 1–4 have good thermal stabilities. Furthermore, 1 and 2 show excellent luminescence in the solid state at room temperature.     

Syntheses,crystal structures and photocatalytic properties of transition metal complexes based on 9,10-anthraquinone-1,3-dicarboxylate

Transition Metal Chemistry - Five transition metal complexes based on the ligand 9,10-anthraquinone-1,3-dicarboxylate acid (1,3-H2AQDC) have been synthesized and characterized by...     

Two copper complexes with imidazole ligands: Syntheses,crystal structures and fluorescence

Two copper (imidazole) complexes, namely, [Cu(im)₆]Cl₂ · 4H₂O (1), and [Cu(im)₆]Cl₂ · 2H₂O (2) (im-imidazole) have been synthesized by hydrothermal method. Single-crystal X-ray analysis revealed that the complex 1 belongs to triclinic system, space group P \(\bar 1\) with a = 8.8097(18) Å, b = 9.0812(18) Å, c = 10.586(2) Å; α = 75.08(3)°, β = 83.14(2)°, γ = 61.84(3)°; R ₁ = 0.0562, wR ₂ = 0.1607. In compound 1, [Cu(im)₆]²⁺ cation and counter anions Cl^? alternatively array in an ABAB fashion via N-H...Cl hydrogen bonding. Compound 2 falls into monoclinic system, space group P2₁/n with a = 8.073(2) Å, b = 13.239(2) Å, c = 15.0810(10) Å; β = 97.940(10)°; R ₁ = 0.0434, wR ₂ = 0.1243. The equatorial ligands are involved into a complex hydrogen bond network that involves the chloride anions and uncoordinated water molecules. We report there synthesis, crystal structure, thermal stability, IR spectrum and fluorescent property.     

Potassium carbazolyl complexes with coordinating solvents: Syntheses and crystal structures

The reaction of carbazole with KOH in dimethylformamide (DMF) at 75°C for 1.5 h affords CarbK(DMF) (CarbH is carbazole) in 90% yield. The crystallization of the compound from DME, CH₃CN, and CD₃CN gives complexes CarbK(DME)₂, CarbK(DMF)(CH₃CN), and CarbK(DMF)(CD₃CN), respectively, whose structures are determined by X-ray diffraction analyses. The dissolution of CarbK(DMF)(CH₃CN) in CD₃CN results in the deuterium exchange in the bound solvent to form complex CarbK(DMF)_0.5(CD₂HCN)_1.5, whose structure is also established by X-ray diffraction analysis.     

Syntheses, electrochemistry and crystal structure studies of novel cis-configuration biferrocene trinuclear complexes

The syntheses and characterization of novel biferrocene trinuclear complexes for Schiff base ligand, S-methyl-N-(ferrocenyl-1-methyl-methylidene)dithiocarbazate (hereafter abbreviate as HL), are described. X-ray diffraction studies established the structures of the palladium complex, PdL₂2 and the copper complex, CuL₂3. The geometry of Pd(II) in 2 is close to square planar and in novel cis-configuration with two ferrocene moieties in the same side, while that of Cu(II) in 3 is close to tetrahedral configuration. Electrochemical measurements suggest that the distorted square planar configuration of the Ni(II) and Pd(II) moieties, can effectively transmit the redox effects of the ferrocene moieties, while the distorted tetrahedral configuration of Cu(II) complex can not transmit the redox effects.     

Syntheses,crystal structures and properties of four metal coordination complexes constructed from aromatic carboxylate and benzimidazole-based ligands

Transition Metal Chemistry - Four metal–organic coordination complexes, namely {[Zn(SIP)(mbi)2]·(Hmbi)·(H2O)2}n (1), {[Cd3(SIP)2(bbhb)3(H2O)4]·(H2O)2}n (2),...     

Syntheses and X-ray structures of some pyrrolylaldiminate metal complexes

Several pyrrolylaldiminate complexes of Group 1, 4 and 13 metals are reported. The reaction of 5-tert-butyl-2-[(2,6-diisopropylphenyl)aldimino]pyrrole (HL) with NaH produced LNa(THF) (1). In situ lithiation of HL followed by addition of one equivalent of MCl_x (M=Zr, x=4; M=Hf, x=4, M=Al, x=3) afforded the corresponding pyrrolylaldiminate complexes, MLCl₂(μ-Cl)₂Li(OEt₂)₂ (M=Zr, 3; Hf, 4) and AlLCl₂ (5). Alkylation of 5 with MeMgBr generated AlLMe₂ (6). In addition to the spectroscopic data, complexes 3-6 were characterized by X-ray crystallography.     

Hydro-ionothermal syntheses, crystal structures, and properties of five new divalent metal iminophosphonates

The use of a moderately hydrophobic ionic liquid, 1-butyl-2,3-dimethylimidazolium tetrafluoroborate ([BdMIM][BF(4)]), as a cosolvent with water, has been investigated in the synthesis of metal phosphonates. This hydro-ionothermal synthesis has been carried out through a systematic combinatorial investigation of several divalent metal chlorides and two related ligands, iminobis(methylphosphonic acid) and N-methyliminiobis(methylphosphonic acid). These reactions resulted in five new divalent metal phosphonates. We present here the synthetic techniques utilized as well as the X-ray structures and characteristic properties of each of these compounds. Co(HO(3)PCH(2)NH(2)CH(2)PO(3)H)(2), (1), consists of sheets that are hydrogen bonded together by pairs of P-O···H groups. Co(H(2)O)(2)(HO(3)PCH(2)NH(2)CH(2)PO(3)H)(2), (2), consists of chains that are connected through an extensive network of hydrogen bonds. Co(HO(3)PCH(2)NH(CH(3))CH(2)PO(3)H)(2), (3), is made up of sheets that are hydrogen bonded together by pairing P-O···H interactions. Zn(3)(O(3)PCH(2)NH(2)CH(2)PO(3))(2), (4), is isostructural to a previously reported cobalt compound which is a non-porous 3-dimensional network. CuClPO(3)CH(2)NH(2)CH(3), (5), formed as a result of an in situ N-C bond cleavage. Ladders built of Cu-O-P-O 8-membered rings are crosslinked by bridging chloride atoms to form sheets. 1, 3, 4 and 5 have been synthesized using the hydrophobic ionic liquid 1-butyl-2,3-dimethylimidazolium tetrafluoroborate ([BdMIM][BF(4)]) with water as a cosolvent, while 2 has been synthesized from identical conditions in the absence of the [BdMIM][BF(4)]. We also report the microwave assisted hydro-ionothermal synthesis of the known polymorph of 2, Co(H(2)O)(2)(HO(3)PCH(2)NH(2)CH(2)PO(3)H)(2), (6), synthesized in two hours providing high quality crystals in good yield. The compounds have been characterized by thermogravimetric analysis and IR spectroscopy, and their magnetic properties have been investigated.     

Syntheses,spectroscopic characterization,thermal behavior,electrochemistry and crystal structures of two novel pyridine metatungstates

Two novel metatungstate compounds [Hdmpy]₄H₂[H₂W₁₂O₄₀]·4H₂O (dmpy?=?2,6-dimethyl pyridine) (1) and [Hpy]₄H₂[H₂W₁₂O₄₀] (py?=?pyridine) (2) have been synthesized by rational reaction, rather than hydrothermal or electrosynthetic reaction, of sodium tungstate dihydrate with 2,6-dimethyl pyridine and pyridine, respectively and characterized by IR and electronic spectroscopies, thermal behavior and electrochemistry. X-ray single-crystal structural analyses indicate that both structures consist of close-packed arrangements of the almost spherical Keggin-type anion [H₂W₁₂O₄₀]^6? with protonated 2,6-dimethyl pyridine or pyridine molecules filling the gap of the polyanions and interacting with the metatungstate anions in the mode of W-O···H-N or W-O···H-C, giving a two-dimensional network structure. The TG-DTA curves of 1 show that weight loss is divided into two stages, and reveal that the framework of the polyanion in 1 begins to decompose at 613°C. Electrochemical study shows that Compound 1 exhibits two chemically quasi-reversible one-electron reduction processes in aqueous solution (0.5?M NaCl?+?HCl) in the pH range 4–7.     

间甲基苯甲酸稀土配合物的合成及晶体结构

本文合成了间甲基苯甲酸与十五种稀土元素的配合物REL3(RE=Y, Ln～Lu;HL=m～CH3C6H4CO2H), 研究了它们的红外光谱并测定了钕和铽两种稀土配合物的晶体结构, 两者均属单斜晶系, 空间群P2~1/n, 钕离子配位数为9, 铽离子配位数为8, 配合物均具有无限链状聚合结构。     

邻氯苯甲酸稀土配合物的合成、表征及结构

本文合成了邻氯苯甲酸与十五种稀土的配合物REL~3·H~2O(RE=Y,La～Lu,L=Clc~6H~4CO~2H),研究了它们的热分解及红外光谱.测定了钕、铽及镥三种稀土的配合物晶体结构,均属单斜晶系,空间群P2~1/n,稀土离子配位数为9,配合物呈无限链状聚合结构.     

Syntheses and crystal structures of two lead complexes containing tricyanomethanide

Two lead complexes [Pb(2,2′-bipy)₂(H₂O)₂(tcm)]₂·(tcm)₂·2H₂O, 1, and [Pb(phen)₂(tcm)₂], 2, have been prepared by reacting Pb(NO₃)₂, potassium tricyanomethanide (Ktcm) and 2,2-bipyridine or 10-phenanthroline, respectively. X-ray crystallography studies show that 1 is a dimer formed by two eight-coordinate [Pb(bipy)₂(H₂O)₂] units bridged by tricyanomethanide while 2 is a mononuclear six-coordinate compound with the lead atom surrounded by two phen ligands and two tricyanomethanide ions.