Crystal structures ofcatena-[diligatocadmium(II) tetra-μ-cyanocadmate(II)] host clathrates: Diamminecadmium(II) tetracyanocadmate(II)-benzene(1/2), diamminecadmium(II) tetracyanocadmate(II)-aniline(1/2), ethylenediaminecadmium(II) tetracyanocadmate(II)-aniline(1/2), and a novel type bis(aniline)cadmium(II) tetracyanocadmate(II)-aniline(2/1)

The crystal structures of the four title clathrate compounds Cd(NH₃)₂Cd(CN)₄ · 2C₆H₆,I, Cd(NH₃)₂Cd(CN)₄ · 2C₆H₅NH₂,II, Cd(NH₂CH₂CH₂NH₂)Cd(CN)₄ · 2 C₆H₅NH₂,III, and Cd(C₆H₅NH₂)₂Cd(CN)₄ · 0.5C₆H₅NH₂,IV, have been analyzed by single crystal X-ray diffraction methods. CompoundI crystallizes in the monoclinic space groupC2/c,a = 12.063(2),b = 12.174(2),c = 14.621(1) Å,β = 90.976(9)°,Z = 4,R = 0.042 for 2388 reflections;II: monoclinic C₂/c,a = 12.1951(9),b = 12.078(1),c = 14.6921(7) Å,β = 93.436(5)°,Z = 4,R = 0.039 for 2374 reflections;III: monoclinicCc,a = 11.027(1),b = 12.0767(9),c = 15.837(1) Å,β = 92.059(9)°,Z = 4,R = 0.041 for 2883 reflections; andIV: monoclinicP2₁/n,a = 15.169(2),b = 16.019(2),c = 8.866(1) Å,β = 95.73(1)°,Z = 4,R = 0.052 for 3612 reflections. The three-dimensionalcatena-[diamminecadmium(II) tetra-μ-cyanocadmate(II)] hosts ofI andII are substantially isostructural to that of the already known Hofmann-Td-type Cd(NH₃)₂Hg(CN)₄ · 2C₆H₆. The three-dimensional en-Td-typecatena-[catena-μ-ethylenediaminecadmium(II) tetra-μ-cyanocadmate(II)] host ofIII, reinforced by the catena-μ-en linking between the octahedral Cd atoms, accommodates the aniline as the guest with a monoclinic distortion from the tetragonal symmetry of the previously reported en-Td-type benzene clathrate. InIV dual behavior of aniline, one as the unidentate ligand in the three-dimensional host and the other as the guest in the cage-like cavity, has been demonstrated.     

Structural characterization of dichloridobis(N,N’-dimethylthiourea-S)cadmium(II)

A cadmium(II) complex, dichloridobis(N,N’-dimethylthiourea-S)cadmium(II), [Cd(Dmtu)₂Cl₂] (1), was prepared and its structure was determined by X-ray crystal structure analysis. The cadmium(II) ion is four-coordinated and the complex has a distorted tetrahedral geometry. The bond angles are in the range of 108.18(3)–110.45(2)°. The metal ion is bonded to two chloride ions and two dimethylthiourea molecules through the sulfur atoms. The crystal structure shows both intra- and intermolecular hydrogen bonds. The new complex was also characterized by IR and NMR spectroscopy and the spectroscopic data are discussed in terms of the nature of bonding.     

Structure of tetra(3,5-dinitrobenzoate) bis(Piperidine) hexaaquanickel(II)—[Ni(OH2)6](PipH)2(3,5-DNB)4·2H2O dihydrate

It is found that M(AmH)₂(3,5-DNB)₄·8H₂O compounds (where M(II) = Co, Ni; AmH is piperidine PipH = (C₅H₁₀NH₂)⁺ or diethylamine DaH = (C₄H₁₀NH₂)⁺ cations; 3,5-DNB = (C₇H₃N₂O₆)⁻ is the dinitrobenzoic acid anion) are isotypic. The structure of the Ni(PipH)₂(3,5-DNB)₄·8H₂O single crystal is studied. The crystals have a monoclinic system, P2₁/n space group, Z = 2, a = 6.7694(3) ?, b = 16.0746(6) ?, c = 23.1250(9) ?, β = 97.794(1)°, V = 2493.1(2) ?³, T = 153 K. The final value R(F) = 0.0407 was obtained for 8191 independent reflections with I> 2σ(I). The structural units of the compound studied are as follows: [Ni(OH₂)₆]²⁺ complex hexaaquacation, two (PipH)⁺ cations, four (3,5-DNB)⁻ anions, and two molecules of water of crystallization with the structural formula [Ni(OH₂)₆](PipH)₂(3,5-DNB)₄·2H₂O. Similar compounds of Ni(II) and Co(II) are isostructural.     

Complexes of N-(thio)phosphorylthioureas AdNHC(S)NHP(X)(OiPr)2 (X?=?O, S) with cobalt(II), zinc(II), and cadmium(II). Crystal structure of Co[AdNHC(S)NP(S)(OiPr)2]2

Reaction of the potassium salts of N-(thio)phosphorylated thioureas of common formula AdNHC(S)N(H)P(X)(OiPr)₂ (Ad = adamantyl; X = O, HL ^I ; X = S, HL ^II ) with Co(II), Zn(II), and Cd(II) cations in aqueous EtOH leads to M(L ^I,II -X, S) ₂ chelate complexes. The Cd(II) complex Cd(L ^I ) ₂ could not be isolated under analogous conditions because of its hydrolytic lability. The structure of the resulting compounds was studied by means of spectroscopy and microanalysis; in addition, the molecular structure of the complex Co(L ^II ) ₂ was elucidated by single crystal X-ray diffraction analysis. The cobalt atom is in a tetrahedral S₄ environment formed by the C=S and P=S sulfur atoms of two deprotonated ligands L ^II . The magnetic properties of Co(L ^I,II ) ₂ were investigated and the photoluminescent properties of the complexes are also reported.     

Metal–radical complexes [M(NITm-Py)2(N3)2(DMSO)2] [M = Cu(II), Ni(II), Co(II)]: Syntheses,crystal structures and magnetic properties

Three new metal–radical complexes of the formula [M(NITm-Py)₂(N₃)₂(DMSO)₂] [M = Cu(II) 1, Ni(II) 2, Co(II) 3; NITmPy = 2-(3′-pyridyl)-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide] were synthesized and characterized structurally as well as magnetically. Three complexes are three-spin complexes in which two NITmPy radical ligands are coordinated to the metal ion through the nitrogen atoms of the pyridyl rings. The magnetic behaviors of the three complexes are investigated. Complexes 1 and 2 show ferromagnetic interactions while antiferromagnetic coupling is predominant for complex 3. The magnetic properties are analyzed in connection with their structures and the magnetic exchange mechanism is discussed.     

Synthesis and crystal structure of new one-dimensional copper(II) complex [Cu4(En)2(μ1,1-N3)4(μ1,1,1-N3)2(μ1,3-N3)2]n

A new polymer azido-bridged copper(II) complex [Cu₄(En)₂(μ_1,1-N₃)₄(μ_1,1,1-N₃)₂(μ_1,3-N₃)₂] _n (I) (En = ethylenediamine) has been synthesized and crystallography characterized. Complex I shows one-dimensional coordination polymeric structure based on a tetranuclear cluster unit [Cu₄(En)₂(μ_1,1-N₃)₄(μ_1,1,1-N₃)₂(μ_1,3-N₃)₂], in which the azido ions display three different bridging modes.     

Trimethylsilyl-functionalised bis(indenyl)iron(II) complexes: solid-state structure of [η-1,3-(SiMe3)2C9H5]2Fe

The synthesis of the bis(η⁵-indenyl)iron sandwich complexes (η⁵-1-SiMe₃-C₉H₆)₂Fe (3a), (η⁵-2-SiMe₃-C₉H₆)₂Fe (3b), [η⁵-1,2-(SiMe₃)₂C₉H₅]₂Fe (4a) and [η⁵-1,3-(SiMe₃)₂C₉H₅]₂Fe (4b), by the reaction of the appropriate lithium indenide salts [prepared from 1-SiMe₃-C₉H₇ (2a), 2-SiMe₃-C₉H₇ (2b), 1,2-(SiMe₃)₂C₉H₆ (2c) or 1,3-(SiMe₃)₂C₉H₆ (2d)] with ferrous chloride (1) in a 2:1 molar ratio is discussed. The solid-state structure of 4b was determined by single-crystal X-ray diffractometry. Complex 4b exists in a gauche conformation, showing that the indenyl ligands are sterically imposed by the bulk of the Me₃Si substituents. The average Fe-C distance is 2.091(3) Å. Cyclovoltammetric studies indicate that 3 and 4 are redox-active with one-electron oxidations [E^1/2=−270 to −360 mV versus Fc/Fc⁺, Fc=(η⁵-C₅H₅)₂Fe].     

PH电位法研究水杨醛缩氨基硫脲与铜(II)、锌(II)、镍(II)、钴(II)、锰(II)及镉(II)的相互作用

本文为了进一步了解具有生物活性的木杨醛缩氨基硫脲在溶液中与常见金属离子的作用本质, 在半微量恒温滴定池上用PH电位法研究了该物质与铜(II)、锌(II)、镍(II)、钴(II)、锰(II)及镉(II)等二价金属离子的配位作用.     

双核Ni(II)配合物[C17H20N4Ni(H2O)Cl]2Cl2•(CH3OH)的晶体结构及其模板合成新配体

采用“一锅煮”方法, 在金属Ni(II)离子作用下, 以2-乙酰吡啶和1,2-丙二胺物质的量比为2∶1进行反应, 得到了一种新的闭环单Schiff碱N₄四齿配体的配合物[C₁₇H₂₀N₄Ni(H₂O)Cl]₂Cl₂•(CH₃OH). 配合物的晶体结构测定表明, 其配位单元为N桥连的双核配合物, 配位单元间再通过氢键连接成一维链状结构.     

β-diketone complexes of manganese(II), cobalt(II), nickel(II) and palladium(II)

Summary The reactions of manganese(II), cobalt(II) and nickel(II) acetates (1 mole) with antipyrine-4-azo--ethylcyanoacetate (HL¹) and antipyrine-4-azo--acetylacetone (HL²) (1 mole) produce complexes of the M(L)₂ type. K₂PdCl₄ (1 mole) reacts with HL¹ and HL² (1 mole) to yield complexes of the general formula PdLCl, the ligands behaving as monobasic tridentates. The electronic spectral and magnetic data show the complexes to be high-spin octahedral, whereas the palladium(II) complexes are diamagnetic square planar. The complexes were characterized by elemental analyses, conductance measurements and i.r. and electronic spectra as well as magnetic susceptibility measurements and thermal (t.g.a. and d.t.a.) analysis.Nuclear Material Authority.     

PH电位法研究水杨醛缩氨基硫脲与铜(II)、锌(II)、镍(II)、钴(II)、锰(II)及镉(II)的相互作用

本文为了进一步了解具有生物活性的木杨醛缩氨基硫脲在溶液中与常见金属离子的作用本质, 在半微量恒温滴定池上用PH电位法研究了该物质与铜(II)、锌(II)、镍(II)、钴(II)、锰(II)及镉(II)等二价金属离子的配位作用.     

双核Ni(II)配合物[C17H20N4Ni(H2O)Cl]2Cl2•(CH3OH)的晶体结构及其模板合成新配体

采用“一锅煮”方法, 在金属Ni(II)离子作用下, 以2-乙酰吡啶和1,2-丙二胺物质的量比为2∶1进行反应, 得到了一种新的闭环单Schiff碱N₄四齿配体的配合物[C₁₇H₂₀N₄Ni(H₂O)Cl]₂Cl₂•(CH₃OH). 配合物的晶体结构测定表明, 其配位单元为N桥连的双核配合物, 配位单元间再通过氢键连接成一维链状结构.     

[Mx(FeCO2)yLz]型配合物的合成、表征及CV性质研究(M＝Cu(II), Co(II), Cd(II), Pb(II);L=THF, Cl-)

［Ｍｘ（ＦｃＣＯ２）ｙＬｘ］型配合物可在ＴＨＦ中通Ｎ２条件下由ＦｃＣＯ２Ｈ和ＭＸ．ｎＨ２Ｏ（Ｘ＝Ｃｌ＾－和Ａｃ＾－）经长时间反应制得。ＩＲ和＾１ＨＮＭＲ谱表明Ｃｕ（Ⅱ）、Ｃｏ（Ⅱ）属螯环配合物，Ｃｄ（Ⅱ）属四面体型配合物，Ｐｂ（Ⅱ）属线型化合物。     

Knoevenagel condensation of [NC-CH2C(O)-NH-CH(CO2Et)-S]2 with ferrocenecarbaldehyde and the activation of the σ(C-S) bond of [(η-C5H5)Fe{(η-C5H4)-CHC(CN)-C(O)-NH-CH(CO2Et)-CH2-S-}]2 induced by palladium(II)

The results obtained from the Knoevenagel condensation between the aldehydes R-CHO {with R=4-MeO-C₆H₄, 4-NO₂-C₆H₄, 4-Cl-C₆H₄, C₆H₅, 2,4,6-Me₃-C₆H₂ or (η⁵-C₅H₅)Fe(η⁵-C₅H₄)} and [NC-CH₂C(O)-NH-CH(CO₂Et)-S]₂ under different experimental conditions are reported. These studies have allowed the isolation and characterisation of three optically pure polyamides of general formula [R-CHC(CN)-C(O)-NH-CH(CO₂Et)-CH₂-S-]₂ with R=4-MeO-C₆H₄ (3a), 4-NO₂-C₆H₄ (3b) or (η⁵-C₅H₅)Fe(η⁵-C₅H₄) (3f). The reactions of 3f with Na₂[PdCl₄] or Pd(AcO)₂ are also studied. The treatment of Pd(AcO)₂ with 3f in a 2:1 molar ratio in refluxing toluene leads to the formation of [(η⁵-C₅H₅)Fe{(η⁵-C₅H₄)-CHC(CN)-C(O)-NH-C(CO₂Et)CH₂}] (5f). Electrochemical studies based on cyclic voltammetry of compounds 3f and 5f are also reported.     

Synthesis, characterization, and crystal structural study of the iron(II) 4,4′-bithiazole complex [Fe(C6H4N2S2)3]2+(NO3?)2

Abstract  

The complex [Fe(C₆H₄N₂S₂)₃]²⁺(NO₃⁻)₂ was prepared from the reaction of 4,4′-bithiazole with Fe(NO₃)₃·9H₂O in methanol. It was characterized by IR, UV-Vis, luminescence, ¹H NMR and ¹³C NMR spectroscopy, and X ray crystallography. The structure was solved in the orthorhombic space group P2₁2₁2₁ with a = 12.1500(5), b = 12.8434(6), c = 16.2222(7) ?, V = 2531.43(19) ?³, Z = 4, and with wR ₂  = 0.0897.     

(C8H8)Sm(C8H8)Na(THF)3的晶体结构

(C_8H_8)Sm(C_8H_8)Na(THF)_3的晶体属单斜晶系,P2_1空间群.晶胞参数为α=12.140(3),b=13.794(3),c=8.944(3)(?),β=111.68(3)°,V=1391.8(7)(?)~3,Z=2,μ=21.93cm~(-1),D_c=1.43g/cm~3,F(000)=610,Mr=598.0。结构经Patterson函数和Fourier技术解出并经最小二乘修正,最终的偏离因子R为0.046.配合物具有双层夹心结构.其中Sm~(3+)和Na~+通过η~8-环辛四烯基连接。     

Au(II)化合物[Au(CH2)2PH2]2X2 (X＝F, Cl, Br, I)的量子化学理论研究

采用从头计算HF, MP2方法和密度泛函理论, 对Au(II)系列化合物[Au(CH₂)₂PH₂]₂X₂ (X＝F, Cl, Br, I)的几何结构、电子结构和振动频率进行了研究. 研究表明Au的5d和6s电子参与Au—Au以及Au—X之间的成键. Au—Au, Au—X键强烈的电子相关作用使HF方法不适于该体系的研究, BP86和B3LYP两种泛函给出较大的Au—Au和Au—X键长, 而MP2方法和局域的密度泛函方法则给出了合理的结构参数. 局域密度泛函方法计算得到的Au—Au键和 Au—X键振动频率也与实验数据符合较好. 还运用含时密度泛函理论计算了[Au(CH₂)₂PH₂]₂X₂的电子激发能, 对分子在紫外-可见光谱范围内的电子跃迁进行了分析, 考察了卤素配体对激发能的影响, 并结合分子轨道能级的变化对此给予了解释.     

Au(II)化合物[Au(CH2)2PH2]2X2 (X＝F, Cl, Br, I)的量子化学理论研究

采用从头计算HF, MP2方法和密度泛函理论, 对Au(II)系列化合物[Au(CH₂)₂PH₂]₂X₂ (X＝F, Cl, Br, I)的几何结构、电子结构和振动频率进行了研究. 研究表明Au的5d和6s电子参与Au—Au以及Au—X之间的成键. Au—Au, Au—X键强烈的电子相关作用使HF方法不适于该体系的研究, BP86和B3LYP两种泛函给出较大的Au—Au和Au—X键长, 而MP2方法和局域的密度泛函方法则给出了合理的结构参数. 局域密度泛函方法计算得到的Au—Au键和 Au—X键振动频率也与实验数据符合较好. 还运用含时密度泛函理论计算了[Au(CH₂)₂PH₂]₂X₂的电子激发能, 对分子在紫外-可见光谱范围内的电子跃迁进行了分析, 考察了卤素配体对激发能的影响, 并结合分子轨道能级的变化对此给予了解释.