Synthesis,crystal structure,thermal decomposition,and explosive properties of [Bi(tza)3] n (tza = tetrazole acetic acid)

A coordination compound based on tetrazole acetic acid (Htza) and bismuth(III), [Bi(tza)₃] _n , was synthesized and characterized by single crystal X-ray diffraction analysis, elemental analysis, FT-IR, and ¹H NMR spectroscopy. The crystallographic data show that the crystal belongs to monoclinic, P2₁/n space group, a?=?0.91968(19)?nm, b?=?0.94869(19)?nm, c?=?1.7824(4)?nm, β?=?101.488(3)°, and Z?=?4. The central bismuth(III) is nine-coordinate by three nitrogens from three tetrazole rings and six oxygens of the carboxylate of another three tza^? ions, with each tza^? tridentate, chelating, bridging coordination. The coordination bonds and the intramolecular hydrogen bonds make the complex pack into a layered structure in polymer form. The thermal decomposition mechanism of the title complex was investigated by DSC and TG-DTG techniques. Under nitrogen at a heating rate of 10°C?min^?1, thermal decomposition of the complex contains two intense exothermic processes between 217.4°C and 530.3°C in the DSC curve; the final decomposed residue at 570°C was Bi₂O₃. Sensitivity tests showed that [Bi(tza)₃] _n was sensitive to impact and flame stimulus.     

Preparation,crystal structure,and thermal decomposition of an azide energetic compound [Cd(IMI)2(N3)2]n (IMI = imidazole)

Cadmium(II) imidazole (IMI) azide [Cd(IMI)₂(N₃)₂]_n (1) was synthesized using imidazole and azide, and was characterized by the elemental analysis and FTIR spectrum. The crystal structure was determined by X-ray single crystal diffraction, and the crystallographic data show that the crystal belongs to orthorhombic, Pba2 space group, α?=?10.780(4) Å, b?=?13.529(5) Å, and c?=?3.6415(12) Å. Its crystal density is 2.080?g·cm^–3. Cd(II) is a six-coordinate with six nitrogens from four imidazoles and two azides with μ–1,1 coordination. The thermal decomposition mechanism was determined based on differential scanning calorimetry (DSC) and thermogravimetry-derivative thermogravimetry (TG-DTG) analysis, and the kinetic parameters of the first exothermic process were studied using Kissinger’s method and Ozawa’s method, respectively. The energy of combustion, enthalpy of formation, critical temperature of thermal explosion, entropy of activation (ΔS ^≠), enthalpy of activation (ΔH ^≠), and free energy of activation (ΔG ^≠) were measured and calculated. In the end, impact sensitivity was also determined by standard method.     

Synthesis, crystal structure and thermal decomposition character of [Zn(CHZ)3][C(NO2)3]2 · (H2O)2 (CHZ = Carbohydrazide)

A new coordination compound [Zn(CHZ)₃][C(NO₂)₃]₂ · (H₂O)₂ was synthesized and characterized by elemental analysis, FTIR and UV spectra, and its crystal structure was determined by X-ray single crystal diffraction. The crystal belongs to the triclinic system, space group . In the asymmetric unit, zinc (II) ion is six-coordinated with three carbonyl oxygen atoms and three terminal nitrogen atoms to form distorted octahedral structure, three CHZ molecules and central metal cation constitute three planar chelate rings which are vertical one to another, and two trinitromethanides are similar to the conformation of C _2v -like. Zinc (II) ions, carbohydrazide ligand molecules, trinitromethanide anions, and lattice water molecules are jointed to a complicated three-dimensional network structure through coordination bonds, electrostatic forces, and extensive hydrogen bonds. The thermal decomposition character and mechanism were tested through DSC, TG–DTG, and FTIR spectra. The results show that the title complex has high energy and good thermal stability.     

Synthesis,crystal structure,and characterization of energetic complex Pb(ATZ)(phen)2 · 3H2O

A new energetic complex, Pb(ATZ)(phen)₂·3H₂O (1) (ATZ = 5,5′-azotetrazolate), was synthesized and characterized by single crystal X-ray diffraction. Crystal data: monoclinic, P2(1)/n space group, a = 8.4545(1) Å, b = 25.846(2)Å, c = 13.096(2)Å, and β = 102.873(2)°. In addition, elemental analysis, IR, and thermogravimetric analysis are presented. Furthermore, the complex was also explored as an additive to promote thermal decomposition of ammonium perchlorate.     

Synthesis and crystal structure of dinuclear nickel (Ⅱ) complex

The crystal structure of Ni(Ⅱ) complex with 3-hydroxyl-1, 5-diazacycloheptane-N, N'-diacetate was determined by X-ray diffraction method. Crystal data for Ni2 (C9H14N2O5)2·2H2O: monoclinic, space group P21/n, a = 1.1717(5), b = 0.9794(3), c = 1.2971(2) nm, β= 96.62(3), V= 1.4786(7) nm3, Dc = 1.377 g/cm3, Z = 2,μ=13.321 cm-1 (Mo-Kα), F(000)=640. The final R and Rw are 0.075 and 0.089 respectively. The Ni(Ⅱ) ion forms 2:2 complex with ligand. Two ligands are bridged by two Ni(Ⅱ) atoms which are bridged by two O atoms. Every Ni(Ⅱ) is coordinated by two N atoms and four 0 atoms. The coordination polyhedron of the Ni(Ⅱ) ion is a distorted octahedron.     

Synthesis,crystal structure and properties of a tetrametallic 3-ferrocenyl-2-crotonic acid-bridged manganese(II) complex [Mn2(phen)4(FCA)2](ClO4)2·H2O

The title complex [Mn₂(phen)₄(FCA)₂](ClO₄)₂·H₂O (1) (FCA = dianion of 3-ferrocenyl-2-crotonic acid, phen = 1,10-phenanthroline) has been prepared, and its structure determined by single crystal X-ray diffraction analysis. The structure consists of a dinuclear cation [Mn₂(phen)₄(FCA)₂]²⁺, non-coordinated perchlorate anions and a water molecule. The two Mn^II ions are separated by 4.374 Å in the cation and are dicarboxylate-bridged by carboxylate ligands containing ferrocenyl units. Each FCA is bound to two Mn^II ions through carboxylate oxygens with the syn–anti bridging mode. The Mn^II ion is coordinated in an octahedral N₄O₂ geometry by two chelate phen ligands and two -carboxylate oxygen atoms. Electrochemical properties of (1) are discussed.     

An oxo-centered carboxylate-bridged trinuclear complex: synthesis,crystal structure,and magnetic properties of [Cr3(μ3-O)(HL)2(H2O)3](ClO4)3

A new complex [Cr₃(μ₃-O)(HL)₂(H₂O)₃](ClO₄)₃, L = 1,4,7-triazacyclononane-N,N′,N′′-tripropionate(tacntp), has been synthesized and structurally characterized. The complex crystallizes in the orthorhombic, space group Pccn, with unit cell parameters a = 18.245(3) Å, b = 18.955(3) Å, c = 27.806(4) Å, α = 90°, β = 90°, γ = 90°. The complex has a trimetallic structure with three metal ions at the corners of a nearly equilateral triangle and the center occupied by a triply-bridging oxygen. Variable-temperature magnetic susceptibility indicates that the total spin value of the ground state is 3/2.     

[Mn(CHZ)3](ClO4)2的制备、晶体结构和应用研究

碳酰肼[1]分子中有5个含孤电子对原子, 因此可作为单齿或多齿配体与多种金属离子配位[2～3]; 而且, 碳酰肼是肼的衍生物, 具有强还原性, 可用作含能材料的组分, 所以, 其配合物在含能材料领域引起了极大的关注[3～9]. 通过高氯酸锰水溶液和碳酰肼水溶液直接化合的方法得到了标题化合物的单晶, 测定了其晶体结构, 并研究了其爆炸性能.     

Synthesis,crystal structure and magnetic properties of an oxamato-bridged heterobinuclear NiIICuII complex [Ni(cyclam)Cu(opba)]2·3DMSO

An oxamato-bridged heterobinuclear Ni^IICu^II complex [Ni(cyclam)Cu(opba)]₂ · 3DMSO (1) has been synthesized, characterized by elemental analysis, infrared spectra and magnetic susceptibility, where cyclam is 1, 4, 8, 11-tetraazacyclotetradecane and opba is o-phenylenebis(oxamato). The complex crystallizes in the triclinic system, space group P 1 with a = 12.006(3) Å, b = 12.783(3) Å, c = 20.977(5) Å, α = 76.634(4)°, β = 75.172(4)°, γ = 80.818(4)° and Z = 2. According to X-ray crystallographic studies, the four-coordinate copper(II) atom is a slightly distorted planar geometry and is linked to nickel(II) through the exo-cis oxygen atoms of [Cu(opba)]^2?; the six-coordinate nickel(II) center lies in a highly distorted octahedral environment. Magnetic susceptibility measurements of the complex in the temperature range 2–300 K indicate that the heterobinuclear Ni^IICu^II units are coupled antiferromagnetically with J = ?57.38 cm^?1, g _Ni = 2.25 and g _Cu = 2.02.     

Synthesis, crystal structure, magnetic property and thermal studies of [Ni(CH(3)COO)2·(NH2CH2Ph)4

[Ni(CH(3)COO)(2)·(NH(2)CH(2)Ph)(4)] complex was synthesized using benzylamine and nickel acetate. The molecular structure of this complex was obtained by single crystal X-ray diffraction and characterized by elemental analysis, IR spectrometry and thermal analysis. The complex crystallized in the monoclinic space group P2(1)/n with cell parameters a=11.234(4)?, b=6.459(2)?, c=22.647(8)?, α=90.00, β=91.149(4)°, γ=90.00, V=1642.8(10)?(3), Z=2. The structure has been solved by direct methods and refined to R(1)=0.0876 for 6377 observed reflections I>2σ(I). Magnetic studies for complex show the data over the whole temperature range 5-300 K are well fitted to the Curie-Weiss law with C=1.03 cm(3) K mol(-1) and θ=-1.38 K. This fitting indicates antiferromagnetic interaction between the Ni ions and the metal center exhibits distorted octahedral coordination geometries. The thermal analysis was carried out to understand the thermal stability of the title complex.     

Synthesis and crystal structure of a mixed-ligand bismuth(III) complex, [Bi2(phen)2Br5(NO3)] n (phen = 1,10-phenanthroline)

Complex [Bi₂(phen)₂Br₅(NO₃)] _n has been synthesized by reaction of Bi(NO₃)₃ with potassium bromide and 1,10-phenanthroline. The complex has been isolated and characterized by IR-, ¹H NMR-, ¹³C NMR spectrum and elemental analysis. The structure of the [Bi₂(phen)₂Br₅(NO₃)] _n was confirmed by X-ray crystallography which shows the complex to be a one-dimensional polymer as a result of bridging bromides. The two Bi atoms have different environments, six and seven coordinate.     

Synthesis,characterization, and X-ray crystal structure analysis of Cd(ΙΙ) and Cu(II) complexes of an acyclic pentadentate Schiff base

Cd(ΙΙ) and Cu(II) complexes of an acyclic pentadentate Schiff base were prepared by template condensation of two equivalents of 2-acetylpyridine with one equivalent of bis(3-aminopropyl)amine in methanol. The resulting complexes [CdL(NO₃)]ClO₄ (1) and [CuL](ClO₄)₂ · CH₃CN (2) were characterized by X-ray crystallography, elemental analysis, IR and mass spectrometry in both cases and by NMR in the case of 1. The X-ray crystallographic structure determination of these complexes revealed six-coordinate distorted octahedral geometry for 1, with the sixth coordination by nitrate and five-coordinate for 2 with trigonal-bipyramidal Cu(II).     

Synthesis and crystal structure of Co(III) dioximates with the complex anion [SbF6]?

The complexes [Co(DioxH)₂L₂][SbF₆] · nH₂O, where DioxH is dimethylglyoxime monoanion (DioxH^?) or 1,2-cyclohexanedione dioxime (NioxH^?), L is aniline (An) or triphenylphosphine (PPh₃), were isolated from the CoX₂ · nH₂O-NaSbF₆-DioxH₂-L system (X = F or CH₃COO) in aqueous methanol. The complexes were studied by UV, IR, and NMR spectroscopy and by X-ray diffraction. The crystal structure of [Co(DH)₂(An)₂][SbF₆] · H₂O (I) and [Co(NioxH)₂(PPh₃)₂][SbF₆] (II) is stabilized by the electrostatic interactions between the Co(III) complex cations and outer-sphere fluorine-containing anions and by hydrogen bonds between structural units.     

Synthesis and crystal structure of a novel trinuclear Schiff base cadmium(II) complex [Cd3L4] · 2ClO4 · 2CH3OH with antimicrobial activity

The Schiff base 2-ethoxysalicylaldehydethiosemicarbazone (HL) derived from 3-ethoxysalicylaldehyde and thiosemicarbazide and its centrosymmetric trinuclear cadmium(II) complex [Cd₃L₄] · 2ClO₄ · 2CH₃OH (I), have been successfully prepared. The structure of complex I was characterized by elemental analysis, IR spectrum, and single crystal X-ray crystallographic determination. The complex crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 15.584(2), b = 19.540(2), c = 20.994(3) Å, β = 106.632(2)°, V = 6125.2(13) ų, Z = 4, R ₁ = 0.0558, and wR ₂ = 0.1696. The Schiff base coordinates to the Cd atoms through the phenolate O, ether O, imino N, and S atoms. The central Cd atom of complex I is coordinated by eight O atoms from four Schiff base ligands. The terminal Cd atoms of the complex are coordinated by six donor atoms from two Schiff base ligands. The effect of the complex on the antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Candida albicans were studied.     

[Ru(NH3)6](MoO4)Cl·3H2O and [M(NH3)6](ReO4)3·2H2O (M = Ru, Ir). Synthesis and crystal structure

X-ray crystallographic analysis is used to determine the crystal structures of [Ru(NH₃)₆](MoO₄)Cl·3H₂O and [M(NH₃)₆](ReO₄)₃·2H₂O (M = Ru, Ir) complex salts. The features of the fragment packing are studied.     

Hydrates [Na2(H2O)x](2-thiobarbiturate)2 (x = 3, 4, 5): crystal structure,spectroscopic and thermal properties

The hydrates [Na₂(H₂O)₃(Htba)₂] (1) and [Na₂(H₂O)₄(Htba)₂] (2), where H₂tba is 2-thiobarbituric acid, were obtained under different thermal conditions from aqueous solutions and were structurally characterized. The molecular and supramolecular structures were compared to the known structure of [Na₂(H₂O)₅(Htba)₂] (3). In polymeric 1–3, the Htba^? ions are linked to Na⁺ through O and S forming octahedra. The decrease of the number of coordination water molecules led to an increase of the total number of bridge ligands (μ₂-H₂O, Htba^?) and a change of the Htba^? coordination. These factors induced higher distortion of the octahedra. It was assumed that hydrates, with a different number of coordinated water molecules, are more probable when the central metal has weaker bonds with O water molecules and with other ligands. The net topologies of 1–3 were compared. Thermal decomposition and IR spectra were analyzed for 1 and 2.     

Synthesis,crystal structure and photo-induced isomerization of [ N,N ′- bis (4-fluorobenzylidene) ethylenediamine]bromo(triphenylphosphine)copper(I) complex

Abstract

The electrochemical behavior of VOQ₂OH or [VOQ₂-OVOQ₂] (Q = 8-hydroxyquinohnate anion) has been investigated by cyclic voltammetry in acetonitnie solutions. Although both species exist simultaneously at every condition analyzed, they can be clearly differentiated by this method. The effect of trace amounts of water on the electrochemical behavior is also discussed.