Interaction of heterocyclic thioamides with tellurium(II) and tellurium(IV). Syntheses and crystal structures of bis[2-(2-thioxo-1,3- thiazolidin-3-yl)-4,5-dihydro-1,3- thiazolium]hexabromotellurate(IV) and tris(1- methylimidazole-2-(3H)-thione)tellurium(II) bromide

Reaction of 1,3-thiazolidine-2-thione with tellurium(IV) in hydrobromic acid medium gave the hexabromotellurate, [C₆H₉N₂S₃]₂²⁺[Te^IVBr₆]²⁻ (3). Reaction of 1-methylimidazoline-2-(3H)-thione (L″) with tellurium(IV), in hydrobromic acid medium, gave the mixed-ligand tellurium(II) complex [Te^IIL″₃Br]⁺Br⁻ (4). The structures of [C₆H₉N₂S₃]₂²⁺[Te^IVBr₆]²⁻ (3) and [Te^IIL″₃Br]⁺Br⁻ were determined by single crystal X-ray diffraction methods. In 3 the unit cell contains [TeBr₆]²⁻ anions and two [C₆H₉N₂S₃]⁺ cations. There is no direct bonding between the metal atom and the cations. In the anion only slight angular deviations from the perfect octahedral geometry are observed. The lone pair of electrons on tellurium(IV) is found to be stereochemically inert. In the cation the two five-membered heterocyclic rings adopt different conformations. In complex 4, in the solid state, the planar [Te^IIL″₃Br]⁺ cation and Br⁻ anion are held together by ionic interactions. In the cation, L″ is bonded to the central tellurium atom through the sulphur atom.     

Crystal and molecular structure of Δ-5,6-diphenyl-5-methoxy-1,2,4-triazacyclohexene-3-thione and Δ-4-methyl-5,6-diphenyl-5-ethoxy-1,2,4-triazacyclohexene-3-thione

Condensation of thiosemicarbazide or N(4)-ethylthiosemicarbazide with 1,2,8,9-tetraphenyl-3,7-diazanona-1,9-dione in the presence of copper(II) acetate in 96% ethanol leads to Δ⁶-5,6-diphenyl-5-methoxy-1,2,4-triazacyclohexene-3-thione, C₁₆H₁₅N₃OS, or Δ⁶-4-methyl-5,6-diphenyl-5-ethoxy-1,2,4-triazacyclohexene-3-thione, C₁₈H₁₉N₃OS. For C₁₆H₁₅N₃OS the crystal data are monoclinic, P2₁/c, a=9.7780(7), b=8.5120(3), c=18.2210(13) Å, β=100.958(3)°, V=1488.89(16) ų, and Z=4 in agreement with an earlier report. For C₁₈H₁₉N₃OS the crystal data are orthorhombic, P2₁2₁2₁, a=8.6940(3), b=12.9946(3), c=15.5139(5) Å, V=1752.68(9) ų, and Z=4.     

新型金属-双二硫杂戊烯(M-BDT)配合物的合成、表征及X射线的指标化

合成了4个新型NiBDT配位化合物,BDT为具有9个S原子的杂戊烯.元素分析、IR谱、UV谱确定这4个新配合物的化学式分别为[(CH₃)₄N]₂[Ni(C₅S₉)₂](1),[(C₂H₅)₄N]₂·[Ni(C₅S₉)₂](2),[(C₄H₉)₄N]₂[Ni(C₅S₉)₂](3),[(C₆H₅)(CH₃)₃N]₂[Ni(C₅S₉)₂](4).采用Ito法对配合物1的X射线粉末图进行了指标化,确定该晶体属单斜晶系,简单晶格,晶胞参数:a=0.680nm,b=0.714nm,c=2.302nm,γ=111.4°,Z=2.     

2,4-二硫代尿嘧啶的紫外吸收光谱和共振拉曼光谱

硫代嘧啶碱基是光动力疗法潜在的重要光敏剂,其最低单重激发态的光物理研究已有广泛报道。然而,其较高激发态的跃迁性质和反应动力学研究较为稀少。因此,本文采用共振拉曼光谱和密度泛函理论计算方法研究2,4-二硫代尿嘧啶的紫外光谱和几个较高单重激发态的短时结构动力学。首先,基于共振拉曼光谱强度与电子吸收带振子强度f的关系,将紫外光谱去卷积成四个吸收带,分别为358 nm(f=0.0336)中等强度吸收带(A带),338 nm(f=0.1491)、301 nm(f=0.1795)和278 nm(f=0.3532)强而宽的吸收带(B、C和D带)。这一结果既吻合密度泛函理论计算结果,又符合共振拉曼光谱强度模式对紫外光谱带的预期。据此,去卷积得到的四个吸收带被分别指认为S0→S2跃迁、S0→S6跃迁、S0→S7跃迁和S_0→S_8跃迁。同时,分别对B,C和D带共振拉曼光谱进行了详细的指认,获得了短时动力学信息。结果表明,S_8态短时动力学的显著特征是在Franck-Condon区域或附近发生了S8(ππ~*)/S(nπ~*)势能面交叉引发的、伴随超快结构扭转的非绝热过程。S7和S6态短时动力学的主要特征是反应坐标的多维性,它们分别沿C_5C_6/C_2S_8/C_4S_(10)/N_2C_3+C_4N_3H_9/N_1C_2N_3/C_2N_1C_6/C_6N_1H_7/C_5C_6H_(12)和C_5C_6/N_3C_2/C_4S_(10)/C_2S_8+C_6N_1H_7/C_5C_6H_(12)/C_5C_6N_1/C_5C_6H_(12)/C_2N_1C_6/N_1C_2N_3/C_4N_3H_9/N_1C_2N_3等内坐标演化。     

Thermal decomposition study on mixed ligand thymine complexes of divalent nickel(II) with dianions of some dicarboxylic acids

Thermal decomposition of mixed ligand thymine (2,4-dihydroxy-5-methylpyrimidine) complexes of divalent Ni(II) with aspartate, glutamate and ADA (N-2-acetamido)iminodiacetate dianions was monitored by TG, DTG and DTA analysis in static atmosphere of air. The decomposition course and steps of complexes [Ni(C₅H₆N₂O₂)(C₄H₅NO₄)²⁻(H₂O)₂]·H₂O, [Ni(C₅H₆N₂O₂)(C₅H₇NO₄)²⁻(H₂O)₂]·H₂O and [Ni(C₅H₆N₂O₂)(C₆H₈N₂O₅)²⁻(H₂O)₂]·1.5H₂O were analyzed. The final decomposition products are found to be the corresponding metal oxides. The kinetic parameters namely, activation energy (E*), enthalpy (ΔH*), entropy (ΔS*) and free energy change of decomposition (ΔG*) are calculated from the TG curves using Coats–Redfern and Horowitz–Metzger equations. The stability order found for these complexes follows the trend aspartate > ADA > glutamate.     

Thermal studies of novel molecular perovskite energetic material (C6H14N2)[NH4(ClO4)3]

(C6H(14)N2)[NH4(ClO4)3] is a newly developed porous hybrid inorganic-organic framework material with easy access and excellent detonation performances,however,its thermal properties is still unclear and severely hampered further applications.In this study,thermal behaviors and non-isothermal decomposition reaction kinetics of(C6H(14)N2)[NH4(ClO4)3] were investigated systematically by the combination of differential scanning calorimetry(DSC) and simultaneous thermal analysis methods.In-situ FTIR spectroscopy technology was applied for investigation of the structure changes of(C6H(14)N2) NH4(ClO4)3]and some selected referents for better understanding of interactions between different components during the heating process.Experiment results indicated that the novel molecular perovskite structure renders(C6H(14)N2)[NH4(ClO4)3] better thermal stability than most of currently used energetic materials.Underhigh temperature s,the stability of the cage skeleton constructed by NH4^+and ClO4^-ions determined the decomposition process rather than organic moiety confined in the skeleton.The simple synthetic method,good detonation performances and excellent thermal properties make(C6H(14)N2)[NH4(ClO4)3] an ideal candidate for the preparation of advanced explosives and propellants.     

Synthesis and X-ray structure of the Mo(VI) species Mo4O12(C12H30N4S2)2(C3H7ON)n (n ≈ 2)

Dissolution of Mo₂O₅((CH₃)₂NCH₂CH₂NHCH₂CH₂S)₂ in dimethylformamide results in the formation of a species without coordinated sulphur, as indicated by ⁹⁵Mo NMR spectroscopy. Subsequent crystallization of this solution yielded the compound Mo₄O₁₂(C₁₂H₃₀N₄S₂)₂(C₃H₇ON)₂ which X-ray crystallography shows to consist of a novel Mo₄O₁₂ core, containing an eight-membered Mo₄O₄ ring with the two pairs of diagonal molybdenum atoms linked by disulphido-containing groups.     

Hydrothermal Syntheses,Crystal Structures and Thermal Properties of Two New Organically Templated Open-framework Gallium Phosphites

Two new open-framework gallium phosphites formulated as (C₂N₂H₁₀)_0.5Ga₂(OH)(H₂O)(HPO₃)₃(1) and (C₃N₂H₅)₂(C₃N₂H₆)Ga₈(H₂O)₆(HPO₃)₁₄(2) were hydrothermally synthesized in the presence of ethylenediamine(en) and imidazole as structure directing agents(SDA), respectively. Structural analyses reveal that the 3D structures of compounds 1 and 2 are both built up from the linkage of GaO₆, GaO₅(H₂O) and HPO₃^2? units by sharing vertices. The structure of compound 2 is constructed from well-known 4.6.12-net connecting layers in the AAAA stacking sequence, which are penetrated by the 1D Ga-O-P chains to form a 3D pillared-layered structure.     

基于2-氨基吡啶的两个簇基超分子化合物的合成、结构及催化性能

以磷钼酸、2-氨基吡啶、五氧化二钒、氯化锌和氯化镍等为主要原料,采用水热方法合成了2个簇基超分子化合物[H₃PMo₁₂O₄₀]₂[C₅H₆N₂]₆(1)和[H₂PMo₁₂V₂O₄₂][C₅H₆N₂]₅·3H₂O(2)(C₅H₆N₂=2-氨基吡啶).通过元素分析、红外光谱、紫外-可见光谱、X射线光电子能谱、热重分析、X射线单晶衍射及X射线粉末衍射等手段对化合物进行了结构表征.结构分析显示,簇单元不同的2个超分子化合物以各自独特的堆积方式形成三维超分子网络.利用苯乙烯的环氧化反应研究了2个化合物的催化性能.     

X-ray crystal structure and vibrational spectra of hydrazides and their metal complexes. Part II. Hexaaquacobalt(II)bis(phthalhydrazidato)tetrahydrate

The hexaaquacobalt(II)bis(phthalhydrazidato)tetrahydrate, [Co(H₂O)₆](C₈N₂O₂H₅)₂·4H₂O is examined using single crystal X-ray diffraction analysis. The crystals are triclinic, space group , with a = 9.757(1), b = 10.955(2), c = 11.106(1),  = 100.79(2), β = 90.35(3), γ = 91.54(1) and Z = 2. In [Co(H₂O)₆](C₈N₂O₂H₅)₂·4H₂O, the cobalt(II) is coordinated by six water ligands and the [Co(H₂O)₆]²⁺ is associated with the two O-deprotonated phthalhydrazidato ions only by hydrogen bonds. The infrared and Raman spectra of phthalhydrazide (PH) and infrared spectra of deuterated derivative phthalhydrazide (PD) and of [Co(H₂O)₆](C₈N₂O₂H₅)₂·4H₂O are reported. The theoretical wavenumbers, infrared intensities and Raman scattering activities have been calculated using density functional (B3LYP) method with the 6-311++G(d,p) basis set. The calculated potential energy distribution has proved to be of great help in assigning the spectra PH, its deuterated derivative and [Co(H₂O)₆](C₈N₂O₂H₅)₂·4H₂O. The results from natural bond orbital (NBO) analysis for keto-hydroxy form of PH are presented.     

Studies of N-heterocyclic compounds with triosmium clusters: Formation of the heterocyclic-linked dicluster compound [Os 6(μ-H)2(μ3-C6H4N3)2(CO)18]

The cluster [Os₃(CO)₁₀(MeCN)₂] reacts with indazole (C₇H₆N₂) to give two isomeric products [0s₃(μ-H)(μ-C₇H₅N₂)(CO)₁₀] in which the five-membered ring has been metallated with N-H cleavage to give an N,N-bonded isomer or with C-H cleavage to give a C,N-bonded isomer. These two isomers have very similar X-ray structures but can be clearly distinguished by ¹H NMR methods. They are shown to correspond to related clusters derived from pyrazole. Benzotriazole (C₆H₅N₃) also reacts (as shown earlier by others) to give two isomers: an N,N-bonded species [Os₃(μ-H)(μ-C₆H₄N₃)(CO)₁₀] coordinated only through the five-membered ring and a minor C,N-bonded isomer [Os₃(μ-H)(μ-C₆H₄N₃)(CO)₁₀], metallated at the C₆ ring and coordinated through both rings. The former isomer reacts with Me₃NO in acetonitrile to give [Os₃(μ-H)(μ-C₆H₄N₃)(CO)₉(MeCN)] which thermally looses MeCN to produce the coupled product [Os₆(μ-H)₂(μ₃-C₆H₄N₃)₂(CO)₁₈] which was shown by X-ray structure determination to have all six nitrogen atoms coordinated to osmium, a novel situation for coordinated benzotriazole. The two Os₃ units are linked together by an OsNNOsNN ring in a boat conformation with the whole cluster adopting C₂ symmetry.     

Thirty years of organometallic aryldiazenido arylazo derivatives

The aryldiazenido ligands provide the fourth member of the isoelectronic series CO, NO⁺, RNC, RN₂⁺ of ligands for transition metal complexes. The first aryldiazenido metal complex was reported in 1964 when p-CH₃OC₆H₄N₂Mo(CO)₂C₅H₅ was prepared by the reaction of NaMo(CO)₃C₅H₅ with p-CH₃OC₆H₄N₂⁺BF₄⁻. This review surveys the development of organometallic aryldiazenido chemistry since that time. Such organometallic aryldiazenido derivatives, including RN₂M(CO)₂C₅H₅, RN₂M(CO)₂(Pz₃BH) (M = Cr, Mo, W), [(η⁶-Me₆C₆)Cr(CO)₂N₂Ar]⁺, [(MeC₁₅H₄)M′(CO)₂N₂Ar]⁺ M′ = Mn, Re), [trans-PhN₂Fe(CO)₂(PPh₃)₂]⁺, and PhN₂M′(CO)₂(PPh₃)₂(PPh₃)₂ can be obtained by reactions of arenediazonium salts with suitably chosen transition metal nucleophiles. Analogous methods cannot be used to prepare alkyldiazenido transition metal complexes because of the instability of alkyldiazonium salts. However, the alkyldiazenido derivatives RCH₂N₂M(CO)₂C₅H₅ (R = H or Me₃Si) can be obtained from HM(CO)₃C₅H₅ and the corresponding diazoalkanes. Important aspects of the chemical reactivity of RN₂M(CO)₂Q derivatives (Q = C₅H₅, Pz₃BH) include CO substitution reactions, coordination of the second nitrogen in the RN₂ ligand to give heterobimetallic complexes such as C₅H₅Mo(CO)₂(μ-NNC₆H₄Me)(CO)₂C₅H₅, oxidative addition rections with X₂ X = Cl, Br, I), SnX₄, RSSR, and CINO, and reactions with further RN₂⁺ to give bis(aryldiazenido) derivatives (RN₂)₂MQL⁺ (L = CO, X⁻, etc.). Dearylation of an aryldiazenido ligand to a dinitrogen ligand can be effected by reaction of [(MeC₅H₄)M′(CO)₂N₂Ar]⁺ with certain nucleophiles to give (MeC₅H₄)M′(CO)₂N₂.     

Preparation and structure of a ruthenium dicarbonyl derivative of the P2N4S2 ring

The reaction of Ru(CO)₄(C₂H₄) or Ru(CO)₅ with 1,5-Ph₄P₂N₄S₂ in CH₂Cl₂/hexane at 23°C produces the dimer [Ru(CO)₂(Ph₄ P₂N₄S₂)]₂ (2), which was shown by X-ray crystallography to have a centrosymmetric structure in which the P₂N₄S₂ ring is attached to one ruthenium atom through two (geminal) nitrogen atoms and the remote sulfur atom and serves as a bridge to the other ruthenium atom via the second sulfur atom. Crystals of 2 ·2(CH₂Cl₂) are triclinic, space group P (No. 2), a = 12.901(1) Å, b = 13.072(1) Å, c = 10.123(1) Å, = 100.88(1)°, β = 98.90(1)°, γ = 67.50(1)°, V = 1542.4(3) Å, Z = 1 with final R and R_w values of 0.040 and 0.027, respectively.     

A survey of the lone pair effect on the ring geometry of 1,2,4-triazoles and analogous 1,2,3-triazoles and imidazoles : The structures of 1-methyl-5-amino-3-methylthio-1,2,4-triazole, 1-phenyl-5-amino-3-methylthio-1,2,4-triazole and 1-(4-methylbenzyl)-3-amino-5-methylthio-1,2,4-triazole

The structures of the title compounds have been established by X-ray crystallography from diffractometer data. Crystals of the first (I), C₄H₈N₄S, are monoclinic, space group P2₁/c, with a = 8.166(2), b = 10.481(1), c = 8.585(1) Å, β = 109.33(2)°, Z = 4, D_c = 1.381 g cm⁻³. Crystals of the second (II), C₉H₁₀N₄S, are monoclinic, space group P2₁/c, with a = 11.850(4), b = 7.898(1), c = 23.981 (6) Å, β = 117.23(2)°, Z = 8, D_c = 1.373 g cm⁻³. Crystals of the third (III), C₁₁H₁₄N₄S₁ are also monoclinic, space group P2₁/c with a = 12.829(3), b = 8.348(1), c = 11.088(4) Å, β = 94.40(4)°, Z = 4, D_c = 1.314 g cm⁻³. The structures, determined by direct methods (I, III) and Patterson synthesis (II) were refined to R = 0.039 for 1070 reflections of I, R = 0.040 for 2792 reflections of II and R = 0.041 for 1900 reflections of III. The characteristic features of the planar five-membered rings are studied in comparison with the analogous 1,2,3-triazoles and imidazoles. It is shown that these planar rings exhibit only two patterns of the endocyclic bond angles induced dominantly by the number and relative position of the N-lone pairs. A similar effect of the double bonds (attached to C atoms) is also discussed.     

Crystal Engineering of Multiple-component Organic Compound:Organic co-Crystals of the Functional Groups of Carboxyl and Amino with Persistent Hydrogen Bonding Motifs

Three small organic molecular co-crystal compounds (C₃N₆H₆)·(C₆H₁₀O₄)·H₂O(1), C₃H₈N₂O(3) and (H₄btec)₂·(4,4'-bipy)(4)(H₄btec=1,2,4,5-benzenetetracarboxylic acid, 4,4'-bipy=4,4'-bipyridine) and one coordination supramolecular compound [Mn(C₂O₄)(H₂O)₂]·C₆H₁₁NO₂(2) were synthesized by hydrothermal reaction. They were characterized by elemental analysis, infrared(IR) spectroscopy and single crystal X-ray diffraction(XRD). Structural analyses reveal that these 2D or 3D supramolecular networks of the compounds were formed by C―H···O, N―H···O, N―H···N, O―H···O and O―H···N hydrogen bonds. Therein, the functional groups of ―COOH, ―NH₂ and ―OH play important roles in constructing supramolecular architectures.     

Two novel phase transition materials based on 1-isopropyl-1,4-diazabicyclo[2.2.2]octan-1-ium

Two novel phase transition materials,[C₉H₂₀N₂] [Na(BF₄)₃] (1) and[C₉H₂₀N₂] [(PF₆)₂] (2), were synthesized based on 1-isopropyl-1,4-diazabicyclo[2.2.2]octan-1-ium with sodium tetrafluoroborate and hexafluorophosphoric acid, respectively. Differential scanning calorimetry measurements detected that 1 and 2 underwent reversible phase transitions, which were confirmed by dielectric measurements. Single crystal X-ray diffraction data suggested that compound 1 changed from a high temperature phase with a space group of P6₃ to a low temperature one with a space group of P2₁/c, and that compound 2 transformed from the space group of Pbca at room temperature to P2₁/c at low temperature. Formation of hydrogen bonds and distortion of 1,4-diazabicyclo[2.2.2]octane rings may drive the transitions.     

Multi-component Hydrogen-bonding Organic Salts Formed from 1-Methylpiperazine with Aromatic Carboxylic Acids: Synthons Cooperation and Crystal Structures

1-Methylpiperazine was employed to crystallize with 2,4-dihydroxybenzoic acid and 1,8-naphthalene acid, affording two multi-component hydrogen-bonding salts [(C₅H₁₄N₂)²⁺·(C₇H₅O₄)_2-·H₂O](1) and [(C₅H₁₄N₂)²⁺(C₁₂H₆O₄)²ˉ·2H₂O](2). These two forms of salts are both monoclinic systems with space group P2₁/c(14). The lattice parameters of salts 1 and 2 are a=1.32666(10) nm, b=0.90527(7) nm, c=1.67107(13) nm, β=103.125(1)° and a=1.4950(2) nm, b=0.75242(15) nm, c=1.6563(3) nm, β=92.834(2)°, respectively. Expected classical hydrogen bonds N―H…O and O―H…O appear in the chargetransfer salts, and asymmetric units of these two forms both contain water molecules which play a significant role in building novel supramolecular architectures. Robust hydrogen-bond interactions between 1-methylpiperazine and aromatic acid provide sufficient driving force to direct the two crystals to three-dimensional structures. Weak interactions C―H…O emerging in salts 1 and 2 further enhance their crystal structures. As a consequence, hydrogen-bonding interactions in these compounds afford diverse 3D net supramolecular architectures. Thermal stability of these compounds was investigated by thermogravimetric analysis(TGA).     

乙二胺三乙酸与锌(Ⅱ)、钴(Ⅱ)相互作用的固体和溶液化学特性

在水热和弱酸性反应条件下,螯合型表面活性剂前驱体乙二胺三乙酸分别与氯化锌、氯化钴反应,形成水合乙二胺三乙酸金属配合物[M(H₂O)₆][M(ED3A)(H₂O)]₂·2H₂O[M=Zn(1),Co(2);H₃ED3A=乙二胺三乙酸,C₈H₁₄N₂O₆]。 产物经元素分析、红外、热重、液体核磁共振和X射线单晶衍射结构表征。 乙二胺三乙酸和锌(Ⅱ)、钴(Ⅱ)五配位,并与水一起形成典型的[MN₂O₄]或[MO₆]八面体结构。 ¹³C核磁共振实验结果表明,溶液中乙二胺三乙酸与锌形成配合物在弱酸性条件下(pH值3~7)稳定存在,在酸性溶液中完全解离,乙二胺三乙酸进一步经分子内成环反应生成3-酮哌嗪二乙酸(H₂kpda=C₈H₁₂N₂O₅)。     

Temperature-controlled Hydrothermal Synthesis of Copper(I or II) Coordination Polymers via a Variety of Copper Coordination Modes

Two 1D coordination polymers Cu₂^I(C₆N₃H₄)₂(1) and Cu^II(C₆N₃H₄)₂·H₂O(2) based on benzotriazole(Bta) were hydrothermally synthesized by controlling the crystallization temperature. Single-crystal X-ray diffraction (XRD) analyses reveal that compound 1 is a 1D tubular structure constructed from two types of 1D chains {-Cu-N=N-N-}_n, where the Cu(I) ions adopt linear, triangular, and tetrahedral coordination modes to connect two types of Bta ligands via π-π interaction inside the tubular-like chain. For compound 2, the Cu(II) ions assume a quadrilateral coordination mode linking to the Bta ligands to give 1D straight chains, which stacks through π-π interactions to construct a 2D layer structure. Further characterizations including elemental analyses, infrared IR spectra, thermogravimetric(TG) analyses and luminescence properties have been done.     

The reaction of cis dioxobis(2,4 pentanedionato)molybdenum (VI) and 2,2′ pyridylbenzoxazole (L), a novel route to β[Mo8O26]

MoO₂(C₅H₇O₂)₂, where C₅H₇O₂ is 2,4-pentanedione (acac), reacts with 2-2′ pyridylbenzoxazole in acetone to give a product with stoichiometry, Mo₃C₂₄H₁₆N₆O₁₂. This product dissolves readily in dimethylformamide to give a brown solution which on standing for several weeks yielded crystals. An X-ray structure determination showed these crystals to contain uncoordinated 2-2′pyridylbenzoxazole and [(CH₃)₂NH₂]₄⁺[Mo₈O₂₆]⁴⁻.