Studies on three-dimensional coordination polymer [Cd2(N2H4)2(N3)4]n: crystal structure, thermal decomposition mechanism and explosive properties

A 3D coordination polymer of cadmium(II) hydrazine azide, [Cd2(N2H4)2(N3)4]n, was synthesized and characterized by elemental analysis and Fourier transform infrared (FT-IR) spectrum. Its crystal structure was determined by single crystal X-ray diffraction analysis. The crystal belongs to monoclinic, P2(1)/c space group, a=12.555(2)A, b=11.724(2)A, c=7.842(1)A, beta=94.56(2) degrees and Z=4. The crystal contains two crystallographically independent sets of distorted octahedral Cd(II) atoms and dimeric units of Cd2N2, Cd2(NNN)2, Cd2(NN)2 through double micro-1, 1 azide bridges, micro-1, 3 azide bridges and bidentate bridging hydrazine ligands, respectively, and thus generating a 3D network structure. The thermal decomposition mechanism of the complex was studied by using differential scanning calorimetry (DSC), thermogravimetry-derivative thermogravimetry (TG-DTG) and FT-IR techniques. Under nitrogen atmosphere with a heating rate of 10 degrees C/min, the thermal decomposition of the complex contained two intense exothermic decomposition processes in the range of 150-304 degrees C in the DSC curve, and the final decomposed residue at 500 degrees C was Cd. Sensitivity tests revealed that the title complex is very insensitive to external stimuli.     

Geometric isomerism of layered complexes of uranyl selenates: Synthesis and structure of (H3O)[C5H14N]2[(UO2)3(SeO4)4(HSeO4)(H2O)] and (H3O)[C5H14N]2[(UO2)3(SeO4)4(HSeO4)(H2O)](H2O)

New uranyl selenates with organic cations (H₃O)[C₅H₁₄N]₂[(UO₂)₃(SeO₄)₄(HSeO₄)(H₂O)] (I) and (H₃O)[C₅H₁₄N]₂[(UO₂)₃(SeO₄)₄(HSeO₄)(H₂O)](H₂O) (II) were synthesized by evaporation of aqueous solutions and studied. Compound I has monoclinic symmetry, space group C2/c, a = 16.7572(13), b = 11.7239(12), c = 19.0490(13) Å, β = 98.875(6)°, V = 3697.6(5) ų, Z = 4. The crystal structure was solved by the direct method and refined to R ₁ = 0.085 for 2868 reflections with |F _hkl | ≥ 4σ|F _hkl |. Compound II has monoclinic symmetry, space group P2₁/n, a = 10.8252(10), b = 19.0007(10), c = 18.6463(15) Å, β = 100.324(7)°, V = 3773.2(5) ų, Z = 4. The crystal structure was solved by the direct method and refined to R ₁ = 0.084 for 5721 reflections with |F _hkl | ≥ 4σ|F _khl |. The structures of I and II are based on layered complexes [(UO₂)₃(SeO₄)₄(HSeO₄)(H₂O)]^3? formed by combination of uranyl pentagonal bipyramids and selenate tetrahedra. H₃O⁺ cations, water molecules, and protonated methylbutylamine cations are located in the interlayer space. Geometric isomerism of two-dimensional complexes [(UO₂)₃(SeO₄)₅(H₂O)] in the structures of uranyl selenates was found and described.     

Density functional theory calculations for [C(2)H(4)N(2)O(6)]((n)) (n=0, +1, -1)

The structural and electronic properties of neutral and mono ionic structures of isolated ethylene glycol dinitrate (EGDN) [C(2)H(4)N(2)O(6)]((n)) (n=0, +1, -1) have been investigated by performing density functional theory calculations at B3LYP level. The optimum geometry, vibrational frequencies, electronic structure and some thermo dynamical values of the structures considered have been obtained in their ground states. The calculations reveal that as the charge develops the bond lengths and angles change. In the anionic case charge accumulation causes NO(2) elimination as a result of esteric O-N bond cleavage.     

Synthesis, structure, and properties of [Be(H2O)4][UO2(CH3COO)3]2

Crystals of previously unknown compound [Be(H₂O)₄][UO₂(CH₃COO)₃]₂ were prepared and studied by X-ray diffraction analysis. The compound crystallizes in the tetragonal system, unit cell parameters (at 100 K): a = 10.3647(3), c = 23.4127(8) Å, V = 2515.16(13) ų, space group I4₁/a, Z = 4, R = 0.0194. The structure consists of mononuclear complexes [Be(H₂O)₄]²⁺ and [UO₂(CH₃COO)₃]^? linked with each other by electrostatic interactions and hydrogen bonds formed by water molecules and O atoms of acetate anions. The compound was also studied by methods of thermal analysis and IR spectroscopy.     

Thermal polycondensation of ammonium paratungstate, (NH4)10[W12O40(OH)2].4H2O

Connected with the examination of the thermal polycondensation of ammonium paratungstate pentahydrate the chemical and morphological properties of intermediate phases formed during the thermal decomposition of APT have been investigated. We have studied the pH and the turbidity of the aqueous solutions of the intermediate phases, the solubility of the phases, and their rehydratation capability as well as the morphology of the crystallite granules and the grain size distribution. These properties of the original APT have been related to the same properties of the products of decomposition formed between different temperature ranges. The results obtained show unambiguously that each of the above mentioned properties suddenly changes in the temperature range 225 to 250°C. This temperature range coincides with the formation temperature of a new phase called APT II. The most probable formula of APT II is (NH₄)₈ [H₂W₁₃O₄₃(OH)₂]·H₂O.     

Crystal structure, thermal decomposition mechanism and explosive properties of [Na(H2TNPG)(H2O)2]n

The new coordination polymer of sodium trinitrophloroglucinate, [Na(H2TNPG)(H2O)2]n, was synthesized by reacting trinitrophloroglucinol (H3TNPG) with NaHCO3 in aqueous solution and [Na(H2TNPG)(H2O)2]n was recrystallized to be yellow single crystal. The title compound was characterized by using elemental analysis and Fourier transform infrared (FT-IR) spectrum. Its crystal structure was determined by single crystal X-ray diffraction analysis. The crystalline belongs to monoclinic system and C2/c space group. Each Na+ ion is six-coordinated to one H2TNPG- anion and four water molecules in which the oxygen atoms in the water molecules act as bridging atoms. Coordination bonds, electrostatic interaction and intermolecular hydrogen bonds assemble the ions into network structures. The thermal decomposition mechanism of the complex was studied by using differential scanning calorimetry (DSC), thermogravimetry/derivative thermogravimetry (TG/DTG) and FT-IR techniques. Under nitrogen atmosphere with a heating rate of 10 degrees C/min the thermal decomposition of the complex contained one endothermic and five exothermic processes. Two intense exothermic decomposition processes were observed in the range of 173-228 degrees C suggesting its energetic nature and the solid decomposition residue at 500 degrees C was sodium isonitrile. Explosive properties revealed that the compound is sensitive to mechanical stimuli. All properties data observed show that the title compound has explosive properties and can act as components of ecologically clean initiating compositions.     

Phase diagrams of the ternary liquid systems [Ce(NO3)3(TBP)3]-C10H22-[UO2(NO3)2(TBP)2] and [Ce(NO3)3(TBP)3]-C10H22-[Th(NO3)4(TBP)2] and of the quaternary liquid system [Ce(NO3)3(TBP)3]-C10H22-[UO2(NO3)2(TBP)2]-[Th(NO3)4(TBP)2]

The phase diagrams of the ternary liquid systems [Ce(NO₃)₃(TBP)₃]-C₁₀H₂₂-[UO₂(NO₃)₂(TBP)₂] and [Ce(NO₃)₃(TBP)₃]-C₁₀H₂₂-[Th(NO₃)₄(TBP)₂] and of the quaternary liquid system [Ce(NO₃)₃(TBP)₃]-C₁₀H₂₂-[UO₂(NO₃)₂(TBP)₂]-[Th(NO₃)₄(TBP)₂] at T = 298.15 K are constructed. The phase diagrams are characterized by areas of homogeneous solutions and of two-phase liquid systems (systems with phase separation), with one phase (I) enriched in [Ce(NO₃)₃(TBP)₃], [Th(NO₃)₄(TBP)₂], and [UO₂(NO₃)₂(TBP)₂], and the other phase (II), in C₁₀H₂₂. Using the data on the mutual solubility of the components in the systems under consideration and equations of the NRTL model, the parameters of intermolecular interactions and the excess Gibbs energies (G ^ex) were calculated for the binary, ternary, and quaternary systems. Passing from the ternary system [Ce(NO₃)₃(TBP)₃]-C₁₀H₂₂-[Th(NO₃)₄(TBP)₂] to the quaternary system [Ce(NO₃)₃(TBP)₃]-C₁₀H₂₂-[UO₂(NO₃)₂ (TBP)₂]-[Th(NO₃)₄(TBP)₂] does not appreciably affect the distribution of C₁₀H₂₂ between phases I and II, but leads to the redistribution of [Ce(NO₃)₃(TBP)₃] into phase II and of [Th(NO₃)₄(TBP)₂] into phase I.     

A new three-dimensional open-framework iron(III) phosphate, [C2N2H10][Fe2(HPO4)4]

A new open-framework iron(III) phosphate, I, [C₂N₂H₁₀][Fe₂(HPO₄)₄] has been hydrothermally synthesized in the presence of ethylenediamine (en). The structure is built up from the vertex linkages between the FeO₆ octahedra and the PO₄ tetrahedra, strictly alternating, forming the three-dimensional architecture. The linkages between the FeO₆ and PO₄ polyhedra gives rise to ladder-like edge-shared chains, which are connected variously forming two types of channels. The di-protonated en molecules occupy these channels. Crystal data for I, [C₂N₂H₁₀][Fe₂P₄O₁₆]: a=9.341(1), b=8.892(1), c=9.480(1) Å, β=117.6(1)°, V=698.1(1) ų, space group P2/n (No. 13), Z=2, M=557.7, D_calc=2.65 g cm⁻³, MoKα (λ=0.71073 Å), R₁=0.03, wR₂=0.08 and S=1.10. Magnetic susceptibility studies indicate a predominantly antiferromagnetic interaction with T_N=30 K.     

Crystal structure of a new organic dihydrogenomonophosphate (C6H8N3O)2(H2PO4)2

Chemical preparation, X-ray single-crystal, thermal behavior, and IR spectroscopy investigations are given for a new organic cation dihydrogenomonophosphate (C₆H₈N₃O)₂(H₂PO₄)₂ (denoted IAHP) in the solid state. This compound crystallizes in the orthorhombic space group P2₁2₁2₁. The unit cell dimensions are: a = 7.422(3) Å, b = 12.568(5) Å, c = 20.059(8) Å with V = 1871.1(13) Å³ and Z = 4. The structure has been solved using direct method and refined to a reliability R factor of 0.029. The atomic arrangement can be described as inorganic layers of H₂PO₄⁻ anions between which are located the organic groups (C₆H₈N₃O)⁺ through multiple hydrogen bonds.     

Crystal Structure of U(VI) Peroxo Complex with Triphenylphosphine Oxide {(UO2)2O2[OP(C6H5)3]6}(ClO4)2

The peroxo complex {(UO₂)₂O₂[OP(C₆H₅)₃]₆}(ClO₄)₂ was synthesized, and its crystal structure was determined [triclinic unit cell: a = 10.523(2), b = 16.242(3), c = 16.978(3) Å, = 65.79(3)°, = 85.06(3)°, = 77.14(3)°, space group P-1, Z = 1, V = 2580.1(9) ų, d _{c a l c} = 2.789 g cm^{- 3}; CAD4, MoK , graphite monochromator, direct method, R ₁ = 0.0368 for 3115 observed reflections, wR ₂ = 0.1107 for 4403 unique reflections, 622 refined parameters]. {(UO₂)₂O₂[OP(C₆H₅)₃]₆}(ClO₄)₂ has monomeric structure and consists of the complex cations {(UO₂)₂O₂[OP(C₆H₅)₃]₆}^{2 +} and ClO₄ ^- anions. The uranium atom has a pentagonal-bipyramidal oxygen surrounding (CN 7). Uranyl groups UO₂ ^{2 +} are linear and symmetrical, the U = O bond lengths are 1.780(8) and 1.787(8) Å, the O(1) = U = O(2) bond angles are 178.7(4) Å. The equatorial planes of bipyramids are formed by oxygen atoms of three TPPO molecules [U-O_{T P P O} 2.352(8)-2.368(7) Å, average 2.362 Å] and peroxo group O₂ ^{2 -} [U-O_{p e r} 2.285(8) and 2.323(8) Å, average 2.305 Å]. Two pentagonal bipyramids sharing the common edge O(3)-O(3)^(a) form the centrosymmetrical peroxo-bridged diuranyl complex {(UO₂)₂O₂[OP(C₆H₅)₃]₆}^{2 +} with the [UO₂O₂UO₂]^{2 +} core. The length of the O(3)-O(3)^{( 9a )} edge is 1.426(15) Å.     

A new high-nitrogen compound [Mn(ATZ)(H2O)4] x 2H2O: synthesis and characterization

A new high-nitrogen compound [Mn(ATZ)(H(2)O)(4)] x 2H(2)O (ATZ=5,5-azotetrazolate) was synthesized. Crystal structure and elemental, IR and thermal analyses were investigated in the present work. It crystallized in triclinic space group P-1 with lattice parameters a=6.304(2)A, b=7.004(2)A, c=7.921(3)A, alpha=76.114(5) degrees , beta=74.023(5) degrees , gamma=69.254(4) degrees . TG-DTG and DSC measurements are employed to postulate the thermal decomposition mechanism. The thermal decomposition kinetics of the main exothermic reaction was investigated by non-isothermal method and obtained its enthalpy of decomposition and the probable kinetic mechanism. An attempt was made to incorporate the relation between thermal stability and the structure.     

Effects of copper content on the structural and magnetic properties of spinel (Co,Cu)Fe2O4 ferrites

Spinel Co–Cu ferrites with the nominal composition Co_1?x Cu _x Fe₂O₄ ferrites (x = 0.0–0.4 with steps of 0.1) were prepared by a chemical coprecipitaiton and sintering process, and their structural and magnetic properties were studied by using XRD, TGA–DTA, FTIR, SEM and VSM analyses. All the specimens prepared are single phase after sintering at 900 °C for 5 h, and nearly no change of lattice parameter is found. The study of grain size shows that suitable amount of Cu substitution is favorable for the growth of grains, while too much Cu substitution inhibits the growth of grains instead. Also found is that with the increase of x, the saturation magnetization decreases continuously from 76.6 (x = 0.0) to 59.0 emu/g (x = 0.4), while the coercivity exhibits a first decreasing but then increasing tendency.     

Novel photoluminescent mesogenic Schiff-base ligands bearing [N4O4] donors and their bimetallic Zn(II) complexes

Novel photoluminescent salicylaldimine ligands condensed from 3^/, 3^/, 4^/, 4^/-tetraminobiphenyl and 4-substituted long alkoxy salicylaldehyde possessing two sets of tetradentate [N₂O₂] donor site and their binuclear zinc(II) complexes have been synthesized. The mesogenic and photophysical properties were investigated. The compounds were characterized by FT-IR, ¹H and ¹³C NMR, UV–vis, elemental analyses, solution electrical conductivity measurements and FAB mass spectrometry. The mesomorphic behavior of these compounds was probed by differential scanning calorimetry and polarized optical microscopy. The ligand with six carbon chain length showed monotropic nematic mesomorphism at 128° C. However, the ligand with alkoxy tail of carbon length 12 showed enantiotropic SmC phase. The complexes are devoid of any mesomorphism. The low molar conductance values in CH₂Cl₂ indicate that the complexes are non-electrolytes. At 330 nm excitation, the ligand emits green light at ~ 516 nm (Φ = 30%) and ~ 549 nm (Φ = 16%) in solution and solid state, respectively. At similar excitation wavelength, the complexes exhibit blue light in solution at ~ 452 nm (Φ = 20%) and green light in solid state ~ 555 nm (Φ = 11%). The DFT calculations were performed using DMol3 program at BLYP/DNP level to ascertain the stable electronic structure of the complex.     

Synthesis and crystal structure of chlorate-enclathrated in aluminogermanate sodalite Na8[AlGeO4]6(ClO3)2

Encapsulation of chlorate in sodalite with aluminogermanate host framework has been obtained by one pot hydrothermal synthesis at 393 K. The crystal structure of Na₈[AlGeO₄]₆(ClO₃)₂; sodalite was refined from X-ray powder data in the space group P $\bar 4$ 3n: a = 9.169 Å, where Al-O-Ge angle is 137.6°. The ²⁷Al MAS NMR study confirmed alternate Ge and Al ordering of the sodalite framework, while ²³Na gave insight into the structure and dynamics of the cage fillings. Infrared spectrum confirmed the encapsulation of chlorate as well as the framework formation of aluminogermanate sodalite. SEM study showed the retention of cubical morphology of the aluminogermanate sodalite. Thermogravimetric analysis provided information on the extent of chlorate entrapment, stability within the sodalite cages and decomposition properties.     

[Ag(PPh_3)_2(CH_3COO)]_2·3H_2O的合成和晶体结构

将醋酸银和三苯基磷按1∶2摩尔比例进行反应得到化合物Ag(PPh3)2(CH3COO)]2,采用红外光谱、核磁共振、元素分析和单晶X射线衍射的方法,对其结构进行了表征.晶体结构解析结果显示,配合物属单斜晶系,空间群C2/c,a=44.286 8',b=13.269 6',c=24.997 0',α=90.000°,β=105.573°,γ=90.000°,Z=8,R=0.052 0,wR2=0.132 4.