Synthesis,crystal structure,and thermal behavior of dimethylgold(III) acetate

A dimethylgold(III) compound with an acetate fragment [(CH₃)₂AuOCOCH₃]₂ has been synthesized. The complex was identified from the melting point, IR, ¹H NMR, and mass spectrometry data. The temperature dependence of saturated vapor pressure over crystals has been measured and the thermodynamic parameters of sublimation have been determined by Knudsen’s effusion method with mass spectrometric measurements of the composition of the gas phase: ΔH _subl = 100.87 kJ·mol^?1, ΔS _subl = 216.67 J·mol^?1·K^?1. The thermal behavior of the solid compound was investigated by differential thermal analysis. The compound was studied by X-ray diffraction. Crystal data for C₈H₁₈Au₂O₄: a = 12.214(5) Å, b = 14.307(3) Å, c = 7.6635(15) Å; β = 103.39(3)°, Z = 4, d _calc = 2.917 g/cm³, space group P2(1)/c, R = 0.0261. The [(CH₃)₂AuOCOCH₃]₂ dimer complex with an Au...Au distance of 2.989 Å is the structural unit. The gold atom has a square plane environment of two carbon and two oxygen atoms; the Au-O distances vary from 2.118 Å to 2.139 Å. The molecules are arranged in chains linked by van der Waals interactions.     

Thermal properties of dimethylgold(III) 8-hydroxyquinolinate and 8-mercaptoquinolinate

Dimethylgold(III) complexes with 8-hydroxyquinoline Me₂Au(Ox) (I) and 8-mercaptoquinoline Me₂Au(Tox) (II) were synthesized and studied. Complex II obtained for the first time was identified from the elemental analysis, IR, ¹H NMR, and mass spectrometry data. The thermal properties of complexes I, II in condensed state were investigated by thermography. The temperature dependences of the saturated vapor pressure over crystals were measured by the Knudsen effusion method with mass spectrometric recording of the gas phase composition and the thermodynamic characteristics of the sublimation process were determined: for I, log P[Torr] = (14.6 ± 0.3) ? (6.34 ± 0.10) × 10³/(T, K), Δ H _subl ^o = 121.2 ± 1.9 kJ^?1, Δ S _subl ^o = 224.1 ± 4.6 J mol^?1 K^?1 (the temperature interval under study 80–115°C); for II, log P [Torr] = (13.3 ± 0.2) ? (6.30 ± 0.09) × 10³/(T, K), Δ H _subl ^o = 120.5 ± 1.7 kJmol^?1, ΔS _subl ^o = 199.3 ± 3.0 J mol^?1 K^?1 (86–145°C).     

Thermal behaviour of dimethylgold(III) carboxylates

The thermal properties of dimethylgold(III) carboxylates of general formula [(CH₃)₂Au(OOCR)]₂ (R=methyl (1), tert-buthyl (2), trifluoromethyl (3), or phenyl (4)) in solid state have been investigated by the thermogravimetric analysis. The temperature dependences of saturated vapour pressure of complexes have been studied by the Knudsen effusion method with mass spectrometric indication. The thermodynamic parameters Δ_sub H _T ⁰ and Δ_sub S _T ⁰ of the sublimation processes have been calculated. Thermal decomposition of the vapour of complexes 1 and 2 has been studied by means of high temperature mass spectrometry in vacuum, and by-products of decomposition have been determined.     

Properties and X-ray structural study of volatile dimethylgold(III) β-iminoketonates

Three complexes of dimethylgold(III) of a general formula of (CH₃)₂Au(R¹-CNH-CH-CO-R²) involving β-imino-derivatives of acetylacetone (k-acac), trifluoroacetylacetone (k-tfa), and pivaloyltrifluoroacetone (k-pta) are studied for the first time with single crystal X-ray diffraction. Synthesis and properties of these compounds are presented along with thermal properties determined by the DTA technique. The structures of the compounds in question are based on monomeric complexes. Gold atoms have a slightly distorted square-planar coordination involving oxygen and nitrogen atoms of the β-iminoketonate ligand and two methyl groups. Geometrical characteristics of the coordination cores are the following: bond lengths of Au-C_Me fall within 2.008–2.050 Å; average Au-O and Au-N distances are 2.094 Å and 2.068 Å respectively. In the structure of (CH₃)₂Au(k-acac) gold complexes are joined by hydrogen bonds to give infinite chains with the shortest Au...Au separation of 5.396 Å. In the crystals of the fluorinated compounds coplanar molecules make infinite stacks. The shortest intra-stack Au...Au separation of 3.416 Å is observed for the complex of (CH₃)₂Au(k-pta) that possesses the largest thermal stability among the investigated compounds.     

X-ray diffraction study of volatile complexes of dimethylgold(III) derived from symmetrical β-diketones

Crystal chemical investigation of volatile dimethylgold(III) β-diketonates of the general formula (CH₃)₂AuL [L = acetylacetone (acac), dipivalylmethane (dpm), dibenzoylmethane (dbm)] has been carried out for the first time. The synthetic procedure and structural data are reported; differential thermal analysis (DTA) data are given. The structure of the compounds includes monomeric complex molecules arranged as polymeric stack associates. The gold atom has a plane square environment AuO₂C₂ formed by two oxygen atoms of the bidentate (O,O) ligand and two methyl groups. The geometrical characteristics of the coordination units are the following: in all complexes, the Au-O and Au-C_Me bond lengths and O-Au-O chelate angles are 2.070–2.108 Å, 1.989–2.034 Å, and 89.7-93.7°, respectively. The shortest Au-Au distance (3.475 Å) in the stack is observed for the (CH₃)₂Au(dpm) complex.     

Synthesis, properties, and structure of dimethylgold(III) complexes [(CH3)2AuI]2 and (CH3)2AuS2CN(C2H5)2

Volatile diethyldithiocarbamate of dimethylgold(III) was prepared by the interaction of dimethylgold(III) iodide with sodium diethyldithiocarbamate. The complex is examined by the elemental analysis, DTA, IR and electronic spectroscopy. The starting dimeric complex [(CH₃)₂AuI]₂ and a novel monomeric volatile gold(III) complex (CH₃)₂AuS₂CN(C₂H₅)₂ with the AuC₂S₂ coordination core were investigated by single crystal X-ray diffraction for the first time.     

Volatile dimethylgold(III) complex with di-iso-butyldithiophosphinate ligand: synthesis,structure, and thermal behavior in condensed and gas phase

Synthesis and molecular structure of air stable, low-melting dimethylgold(III) complex with dithiophosphinate (CH₃)₂AuS₂PⁱBu² (ⁱBu=CH₂CH(CH₃)₂), its thermal properties, and the features as precursor for the metal–organic chemical vapor deposition of gold films are reported. Thermal behavior of the compound in the condensed and gas phase was studied by thermogravimetric analysis and mass spectrometry. Pathways of heterogeneous thermolysis of the compound to elemental gold are discussed. It was found that α-P–H elimination followed by coupling of two alkenyl groups from the coordinated ligand is one of the main thermolysis pathways in condensed and gas phase.     

Crystal structure and luminescence of europium(III) acrylate

The atomic structure of europium acrylate crystals [Eu₂(Acr)₅OH·3H₂O]·2(0.5H₂O) was studied by X-ray analysis (a = 24.360(3) Å, b = 18.466(2) Å, c = 8.5818(9) Å, β = 96.087(2)°, space group C2/c, Z = 6, ρ_calc = 2.036 g/cm³). The crystal structure involves chains of binuclear [Eu₂(C₃H₃O₂)₅OH·3H₂O] molecules, running infinitely in the [101] direction and having pairs of C₉H₉EuO₇H₂O molecules alternating with C₆H₆EuO₄OH·2H₂O molecules that link the pairs. The infinite chains are linked by hydrogen bonds and van der Waals interactions. The thermal behavior of luminescence of the europium(III) complex is discussed.     

Crystal structure and luminescence of antimony(III) bromide with aniline

The atomic structure of antimony(III) bromide crystals with anilinium was determined by X-ray diffraction analysis of (C₆H₅NH₃)₂SbBr₅ (a = 19.704(3) Å, b = 7.914(1) Å, c = 25.556(4) Å; space group Pbca, Z = 8, ρ_calc = 2.365 g/cm³). The crystal structure consists of infinite chains of [SbBr₅]^2? complex anions formed by sharing six vertices and the anilinium (C₆H₅NH₃)⁺ cations, through which the chains are linked in layers by N-H...Br hydrogen bonds. The geometrical aspects that determine the luminescent spectral properties of the complex are discussed.     

Crystal structure and luminescence of antimony(III) chloride complex with anilinium chloride

Crystal structure of (C₆H₅NH₃)₃[SbCl₅]Cl·H₂O is determined by X-ray analysis (a = 9.4155(13) Å, b = 11.4344(16) Å, c = 13.1584(18) Å, α = 113.483(2)°, β = 90.383(2)°, γ = 97.323(2)°, space group P \(\bar 1\), Z = 2, ρ_calc = 1.642 g/cm³). The crystal structure is based on [SbCl₅]^2? anions, anilinium cations (C₆H₅NH₃)⁺, isolated Cl^? anions, and water molecules. Structural features responsible for spectral and luminescent properties of the complex are discussed.     

Crystal structure and fluorescence spectrum of the complex [Eu(III)(TTA)3(phen)]

The title complex Eu(III)(TTA)₃(phen) (where TTA = thenoyltrifluoroacetone monoanion; phen = 1,10-phenanthroline) has been synthesized in mixed solvents of acetone and ethanol (1:1 volume ratio) and its crystal structure has been determined by X-ray diffraction. The complex crystals are triclinic, space group P 1 (# 2) with cell dimensions of a = 1.32.41 (2) nm, b = 1.5278(4) nm, c = 0.9755(3) nm, α = 92.49 (2)°, β = 102.57(2)°, γ = 91.62(2)°, V = 1.9268(8) nm³, Z = 2, μ (Mo Ka)= 18.77 cm^?1, D_x=1.720 g/cm³. The coordination geometry of Eu atom is a distorted square antiprism, and the encapsulated structure that can meet the structural requirement of the typical europium luminescent sensor. The fluorescence spectrum suggests that the complex is a strong photoluminescent material.     

Vibrational interactions in dimethylgold(III) halides and carboxylates

The far-infrared and Raman spectra of binuclear molecules [Me₂AuX]₂ (X = Cl, Br, I) and [Me₂Au(OOCR)]₂ (R = Me, CF₃, Bu^t, Ph) in the 600–70 cm⁻¹ region are reported. The experimentally measured vibrational frequencies of [Me₂AuX]₂ are in a good agreement with density functional theory predictions. The Au…Au vibrational interactions predicted to be in the 270–60 cm⁻¹ region of [Me₂AuX]₂ far-IR and Raman spectra have been observed. The Raman-active Au…Au vibrations of the [Me₂Au(OOCR)]₂ molecules were found to be in the same region as those of [Me₂AuX]₂. The Au–X stretching modes were observed between 100 and 250 cm⁻¹ in accordance with the DFT predictions. Their frequencies in the IR spectra of [Me₂AuX]₂ increase in the sequence I < Br < Cl while the AuC₂ stretching frequencies decrease in the same order. This fact might be an evidence of the decreasing covalent character of the gold-halogen bridges. The Au–O stretching bands of dimethylgold(III) carboxylates have been observed in the 500–250 cm⁻¹ region, and Au–C stretching frequencies of both [Me₂AuX]₂ and [Me₂Au(OOCR)]₂ compounds have been found between 600 and 500 cm⁻¹.     

具有三重螺旋链的二氯苯氧乙酸铽(Ⅲ)配位聚合物的晶体结构与荧光性质

采用水热法制备了一种新型金属配位聚合物[Tb2(2,4-D)6(2,2'-bipy)2]n(1)(2,4-D=2,4-二氯苯氧乙酸;2,2'-bipy=2,2'-联吡啶),用X-衍射单晶结构分析、红外光谱分析、荧光光谱法对产物进行了结构表征。结构分析表明,标题配合物属于单斜晶系,P2(1)/n空间群,晶胞参数a=2.792(1)nm,b=0.851(3)nm,c=3.335(1)nm,β=113.6470(1)°,V=7.2575(5)nm3,Z=4。金属离子Tb3+处于扭变的四方反棱柱构型中,金属离子之间通过配体2,4-D的羧基的桥联作用,链接成为一维三重螺旋链状配位聚合物。配合物的荧光光谱表明,配合物有望成为潜在的绿光材料。     

具有扩展的双链结构的Mn(III)酰腙配合物的合成和晶体结构

合成了含有水杨醛缩(4-甲氧基)苯氧乙酰腙(以下简写为 H2L)的锰配合物[Mn(L)(acac)-(EtOH)]?H2O (MnC23H29 N2O8, Mr = 516.42)。配合物晶体属三斜晶系, 空间群为 P1, 晶胞参数为:a = 7.6942(3), b = 11.2422(4), c = 14.9230(6) ?, α = 95.656(2), β = 104.848(2), γ = 95.642(2)°, V =1231.37(8) ?3, Z = 2, Dc = 1.393 g/cm3, μ = 0.585 mm–1, F(000) = 540。对于 4374 (I > 2σ(I)) 个可观察点, R = 0.0439, wR = 0.1150。在配合物中, 中心 Mn(III)离子具有扭曲的 NO5八面体配位构型。晶体通过分子内与分子间的氢键作用形成平行排列的无限双链结构。     

Crystal structure of poly(p-benzamide)

Redetermination of the crystal structure of poly(p-benzamide) was made by using newly collected intensity data. The molecular conformation is TCTC, where the internal rotation angles about the N? C bond of the amide group and about the virtual bond of N-phenyl-C are T (trans) and C (cis) conformations, respectively. Two molecular chains pass through a rectangular unit cell with dimension, a = 7.75 Å, b = 5.30 Å, c (fiber axis) = 12.87 Å, and the space group, P2₁2₁2₁-D. The reflection observed at the spacing of 010 may be attributed to the reflection due to another crystal polymorph or the diffuse scattering due to disorder. © 1993 John Wiley & Sons, Inc.     

Synthesis and Crystal Structure of a New Lanthanum(III) 4-Cyanobenzoate Complex

A new dinuclear La(III) complex [La2(4-cba)4[H(4-cba)2]2(phen)2(H2O)4] (4-Hcba = 4-cyanobenzoic acid and phen = 1,10-phenanthroline) 1 has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single- crystal X-ray diffraction. Crystallographic data: C88H58La2N12O20, Mr = 1881.28, triclinic P1, a = 7.518(3), b = 17.033(6), c = 17.551(6), α = 115.333(4), β = 92.9910(10), γ = 99.366(5)°, V = 1985.3(12)3, Z = 1, Dc = 1.574 g/cm3, F(000) = 944 μ = 1.145 mm–1, the final R = 0.0281 and wR = 0.0686 for 6708 reflections with I > 2σ(I). In 1, two nine-coordinated La(III) ions are connected by two 4-cba ligands in a syn-syn bidentate coordination mode, and the other six 4-cba ligands terminate the La(III) ions, resulting in an isolated dinuclear structure. Two different types of intramolecular hydrogen bonds, asymmetrical O-H…O and symmetrical O…H…O, exist in the crystal. The title complex molecules are connected through hydrogen bonds and weak π-π stacking interactions to generate a 2-D layered network. The thermogravimetric analysis of 1 has also been discussed.     

Hydrothermal Synthesis and Crystal Structure of CaIn2(PO4)2(HPO4): An octahedral-tetrahedral framework ternary calcium indium(III) phosphate

The new ternary calcium indium(III) phosphate CaIn₂(PO₄)₂(HPO₄) with mixed octahedral-tetrahedral framework was synthesized through hydrothermal reaction of stoichiometric amounts of CaO and InCl₃ with excess of H₃PO₄ and H₂O at pH = 1. Single crystal x-ray diffraction studies show the compound to crystallize in monoclinic symmetry, space group P2₁/n (#14) with a = 657.08(6), b = 2023.7(2), c = 665.72(7) pm, β = 91.20(1)°, Z = 4 and R = 0.043. The framework is built up of dimers of edge-sharing InO₆ octahedra forming In₂O₁₀ units sharing all their OXO ligands with PO₄ tetrahedra, and HPO₄ groups.     

Crystal structure of the Molybdenum(V) Diphosphate KMoP2O8 isotypic with KNbP2O8

A new molybdenum(V) diphosphate KMoP₂O₈ has been isolated. The single crystal X-ray diffraction study of this phase has shown that it is isotypic with KNbP₂O₈. It crystallizes in the P2₁/n space group a = 5.0862(4), b = 11.720(1), c = 11.486(1) Å, β = 90.91(1)°. The structure of this phase is compared with those of other molybdenum(V) diphosphates. This tunnel structure is described in terms of [MP₂O₈]₈∞ ribbons running along ā, showing close relationships with the titanophosphate NaTiP₂O₇. The existence of one free apex for each MoO₆ octahedron and each P₂O₇ group, respectively, is emphasized, allowing a great flexibility of the structure.     

基于双席夫碱配体的两个锰(III)配合物的合成、晶体结构和抑制脲酶活性

制备了一个双席夫碱N,N′-双(3,5-二氟亚水杨基)-1,3-二氨基丙烷(H_2L)。利用H_2L、醋酸锰和硫氰酸铵或者叠氮化钠在甲醇中反应分别制得了配合物[MnL(NCS)(OH_2)](1)和[MnL(μ_(1,3)-N_3)]_n(2)。通过元素分析、红外光谱、核磁共振氢谱对H_2L和其配合物进行了表征,用单晶X射线衍射测定了配合物的结构。席夫碱配体利用其亚胺基氮原子和酚羟基氧原子与Mn进行配位。硫氰酸根配体利用其氮原子配位,而叠氮根配体利用两端的氮原子以桥联的方式进行配位。在每个配合物中,Mn原子都采取八面体配位构型。测试了H_2L和2个配合物对刀豆脲酶的抑制活性。在浓度为100μmol·L~(-1)时,配合物1对脲酶的抑制率为(52.0±3.1)%,其IC50值为(81.0±3.7)μmol·L~(-1),而配合物2却没有活性。还利用分子对接技术研究了配合物1与脲酶的作用方式。     

Synthesis,Characterization and Crystal Structure of an Unsymmetric Samarium(III) Cryptate

Abstract

The complex [Sm(H₃L)(NO₃)(H₂O)](NO₃)₂ · H₂O was synthesized by the (2+3) condensation of tris(2-aminoethyl)amine with 2,6-diformyl-4-chlorophenol in the presence of Sm³⁺. Its crystal structure has been determined. In the complex the coordination number of Sm³⁺ is nine. A water molecule is encapsulated in the cryptate as a guest, confirmed by electrospray mass spectrometry, thermal analysis and the X-ray crystal structure.