Crystal structure and thermodynamic stability of an acetone solvate of bis(trifluoroacetylacetonato)copper(II)

A solvate [Cu(CF₃COCHCOCH₃)₂(CH₃COCH₃)] has been synthesized and characterized for the first time. According to X-ray structural data (diffractometer X8 APEX BRUKER, radiation MoK _α, T = 150 K), it crystallizes in the monoclinic crystal system, space group P2₁/c, a = 8.9940(4) Å, b = 22.3966(11) Å, c = 8.1884(3) Å, β = 92.705(2)°, V = 1647.59(12) ų, Z = 4, d _calc = 1.725 g/cm³, final R = 0.0272. The structure is molecular. In the equatorial plane the atom Cu(II) is surrounded with four oxygen atoms of two chelating ligands (CF₃COCHCOCH₃)^?; Cu-O distances 1.927–1.937 Å, O-Cu-O angles 86.18–93.30° and 170.18–175.67°. Square coordination of Cu is complemented to the square-pyramidal one by the oxygen atom of an acetone molecule behaving as an axial ligand; Cu-O_acetone 2.342 Å, O-Cu-O_acetone 89.66–100.11°. In the studied compound disorder of one of the chelate ligands implies the co-existance of the molecules in the cis- and trans-configuration in the crystal under ratio 54.6:45.4. In air the solvate rapidly degrades losing acetone, while in a sealed vessel melts around 313 K. Temperature dependence of equilibrium vapor pressure of acetone over the complex was measured with the static spoon gauge technique, thermodynamic characteristics of its dissociation process being derived: [Cu(CF₃COCHCOCH₃)₂(CH₃COCH₃)]_s = [Cu(CF₃COCHCOCH₃)₂]_s + CH₃COCH_3g, ΔH _av ⁰ = 49.6(3) kJ/mol, ΔS _av ⁰ = 152(1) J/(mol K), ΔG _av ⁰ = 4.30(2) kJ/mol.     

Thermal investigation of bis(methoxy-β-diketonates) of copper(II) — novel CVD precursors of copper films. Crystal structure of bis(2,2,6,8-tetramethyl-6-methoxynonan-3,5-dionato)copper(II)

Seven copper(II) bis-chelates derived from novel sterically hindered ligands — methoxy-β-diketones     

Crystal structure and vapor pressure of a copper(II) complex with 2,2,6,6-tetramethyl-4-fluoroheptane-3,5-dione

Synthesis and single crystal X-ray diffraction study were carried out for copper(II) 2,2,6,6-tetramethyl-4-fluoroheptane-3,5-dionate (Bruker AXS P4 automated diffractometer, MoK _α radiation). Crystal data for C₂₂H₃₆CuF₂O₄: a = 5.9165(4) Å, b = 10.2787(7) Å, c = 10.5223(8) Å, α = 81.383(3)°, β = 76.106(3)°, γ = 83.778(3)°, space group P $\bar 1$ , V = 612.42(7) ų, Z = 1, d _x = 1.264 g/cm³. The structure is molecular; the copper atom has a square plane coordination formed by the oxygen atoms of two β-diketonate ligands; the average Cu-O distance is 1.895 Å, ∠O-Cu-O 92.5°. Only van der Waals interactions are realized between the molecules in the structure. The temperature dependences of the saturated vapor pressure were studied by the mass transfer technique, and the standard thermodynamic parameters of sublimation were derived for the complex, ΔH _subl ⁰ = 115.6 ± 1.1 kJ/mol, ΔS _subl ⁰ = 204.9 ± 2.5 J/mol·K.     

Structure and properties of heterocomplex compounds based on lead(II) hexafluoroacetylacetonate and copper(II) β-diketonates

Single crystal X-ray diffraction study has been performed for heterometallic complexes based on lead(II) hexafluoroacetylacetonate and copper(II) β-diketonates. Crystal data for Cu(aa)₂·Pb(hfa)₂: a = 8.741(2) Å, b = 12.124(2) Å, c = 13.741(3) Å, α = 89.70(3)°, β = 89.50(3)°, γ = 75.06(3)°, space group P-1, Z = 2, d _calc = 2.084 g/cm³; for Cu(hfa)₂ Pb(hfa)₂: a = 9.334(2) Å, b = 14.584(3) Å, c = 23.102(5) Å, β = 96.82(3)°, space group P2₁/c, Z = 4, d _calc = 2.338 g/cm³. It is demonstrated that the principal structural motif for these compounds is a chain coordination polymer, which consists of alternating molecules of the complexes. The results of a thermogravimetric study for the compounds are reported.     

Crystal and molecular structure of (hexafluoroacetylacetonato) (pivaloylacetonato)copper(II)

The crystal structure of (hexafluoroacetylacetonato)(pivaloylacetonato)copper(II) has been determined. Crystal data for CuO₄C₁₃H₁₄F₆: a = 8.288(2) Å, b = 8.682(2) Å, c = 12.307(2) Å; α = 90.75(3)°, β = 94.29(3)°, γ = 106.60(3)°; V = 845.7(3) ų, space group \(P\overline 1 \), Z = 2, d_calc = 1.617 g/cm³. The coordination polyhedron of the copper atom is formed by four oxygen atoms of two different β-diketonate ligands with Cu-O distances within 1.874–1.946 Å; the O-Cu-O bond angles are 94.8° and 90.6°. The complexes are united into centrosymmetrical “dimers” with Cu...Cu distances of 4.365 Å.     

Crystal structure and thermal investigation of bis-(1-thenoyl-4,4,4-trifluorobutan-1,3-dionato) lead(II)

Lead(II) complex with thenoyltrifluoroacetone has been prepared and characterized by IR spectroscopy, powder and single crystal X-ray diffraction. Crystal data for PbO₄S₂F₆C₁₆H₈: a = 20.457(4) Å, b = 11.292(2) Å, c = 8.409(2) Å; β = 91.37(3)°, space group C2/c, Z = 4, d _calc = 2.222 g/cm³. The molecule of the complex is non-planar, average distances Pb-O are 2.384 Å, chelate angle O-Pb-O is 75.0°. The structure is of polymeric chain nature, Pb...Pb separation in the chains being 4.311 Å. The complex Pb(ttf)₂ is stable under heating up to 250°C. The compound is less volatile than Cu(ttf)₂ or Fe(ttf)₃.     

Synthesis,Crystal Structure and Thermal Stability of a One-dimensional Chain Cobalt Coordination Polymer [Co(4,4'-bipy)(2,4,6-TMBA)_2(CH_3CH_2OH)_2]_n

A one-dimensional chain cobalt(Ⅱ) coordination polymer with 2,4,6-trimethylbenzoic acid, 4,4'-bipyridine and cobalt perchlorate anhydrous has been synthesized and characterized in the mixture solvent of water and alcohol. Crystal data for this complex: monoclinic, space group C2/c, a = 2.3805(8), b = 1.1464(4), c = 1.5807(5) nm, γ = 128.435(4)°, V= 3.3791(18) nm3,Dc = 1.246 g/cm3, Z = 4, F(000) = 1340, final GooF = 1.009, R = 0.0504 and wR = 0.1287.Structural analysis shows that the cobalt ion is coordinated with two nitrogen atoms of one 4,4'-bipyridine molecule and four oxygen atoms from two 2,4,6-trimethylbenzoic acid molecules and two alcohol molecules, giving a distorted octahedral coordination geometry. The result of TG analysis indicates that the title complex is stable till 200 ℃.     

Vapor pressure and crystal structure of platinum(II) <Emphasis Type="Italic">trans</Emphasis>-bis-(trifluoroketoiminate)

The temperature dependence of the saturated vapor pressure of the trans-Pt(ktf)₂ complex obtained from fluorinated β-ketoimine (CF₃-CO-CH₂-C(NH)-CH₃) was studied by the flow method. The standard thermodynamic parameters ΔH ₀ ^T and ΔS ₀ ^T of sublimation have been determined. Full crystal-chemical study has been performed for the complex. Crystal data for C₁₀H₁₀F₆N₂O₂Pt: a = 5.9790(8) Å, b = 7.373(2) Å, c = 8.5767(2) Å,α = 84.05(2)°, β = 72.43(1)°, γ = 67.14(1)°, V = 332.1(1) ų, Z = 1, d_calc = 2.496 g/cm³, triclinic, space group \(P\bar 1\). The structure is molecular and consists of isolated trans-Pt(ktf)₂ complexes. The Pt atom lies at the symmetry center and has a square planar environment of two oxygen and two nitrogen atoms; the distances Pt-O (1.984 Å) and Pt-N (1.969 Å) are similar within the limits of 2σ; the OPtN bond angle is 93.9°. Molecular packing in crystal is considered based on structural data; van der Waals energy of the crystal lattice of trans-Pt(ktf)₂ was calculated by the atom-atom potential method.     

Trans-, cis-isomers of (1,1,1-trifluoro-2,4-pentandionato)Pt(II): Volatility, structure and crystal lattice energy

Trans-and cis-complexes of platinum(II) with trifluoroacetylacetone (Pt(tfa)₂) have been prepared and studied. The synthesis and the separation technique for the isomers are described. Temperature dependencies of saturated vapor pressure measured with a spoon gauge are reported for the cis-Pt(tfa)₂ and trans-Pt(tfa)₂ complexes. The isomers show a significant difference in volatility. The structural study of Pt(tfa)₂ isomers has been performed. Molecular packings in the crystal of each isomer are considered on the base of structural data. The calculation of van der Waals energy of the crystal lattice of cis-Pt(tfa)₂ and trans-Pt(tfa)₂ was made by the atom-atom potential technique, their values being compared with experimental ΔH _T ⁰ values of sublimation for the complexes.     

Investigations into the preparation of sila-β-diketones via 2-trimethylsilyl-1,3-dithianes: structural characterization of a second polymorph of bis(2,2,6,6-tetramethyl-2-sila-3,5-heptanedionato)copper(II)

The sila-β-diketone, 2,2,6,6-tetramethyl-2-silaheptane-3,5-dione (tmshdH), was synthesized by the condensation of the anion of 2-trimethylsilyl-1,3-dithiane with 1-bromo-3,3-dimethylbutan-2-one, followed by unmasking of the latent carbonyl moiety with HgO/HgCl₂. A monoclinic polymorph of the known copper(II) complex, Cu(tmshd)₂, was crystallized and studied by X-ray diffraction methods and found to be disordered like the orthorhombic one. Attempts to synthesize the disilylated β-diketone, 2,2,6,6-tetramethyl-2,6-disilaheptane-3,5-dione and monosilylated 4,4-dimethyl-4-sila-3-oxo-pentanal using the dithiane method were not successful. However, the 1,3-dithianyl precursors, along with the impurity 2,2^′-bis(trimethylsilyl)-2,2^′-bi-1,3-dithiane, were studied crystallographically. Large stereoelectronic and steric effects on the solid-state bonding parameters were observed for these molecules.     

配合物形成的三维超分子体系—[Ni(C_6H_4O_2N)_2(H_2O)_4]的水热法合成、晶体结构及热分析

采用水热法用Ni(NO3)26H2O和异烟酸制备出了一种新的由配合物形成的三维超分子体系—[Ni(C6H4O2N)2(H2O)4],并通过X射线衍射对其晶体结构进行了测定。 该晶体属三斜晶系,空间群为Pī, 所得晶胞参数为: a = 6.9228(4), b = 9.6664(19),c = 6.322(1) , a = 96.86(3), b = 113.33(3), g = 110.35(3)°, V = 347.6(1) 3, Z = 1, Mr = 374.98, Dc = 1.791 g/cm3, F(000) = 194, m = 1.443 mm-1。用1362个可观察的 (I > 2s(I))衍射点,修正123个结构参数, 最终偏离因子R = 0.0444,wR = 0.1271。在组成该化合物的基本结构单元[Ni(C6H4O2N)2(H2O)4]中,Ni处于1个稍微拉长的八面体的中心; 各个结构单元之间通过氢键OH…O相互连接,形成了无限伸展的具有层状结构的三维超分子体系。 另外,从差热及热重曲线可以看出,该化合物加热到154 ℃时开始分解, 首先失去4个H2O,再失去2个异烟酸根,最后残余物为NiO。     

Structure and Thermal Stability of a One-dimensional Chain Cobalt Coordination Polymer [Co（phen）（2,4,6-TMBA）2（H2O）]n

A one-dimensional chain cobalt(II) coordination polymer with 2,4,6-trimethyl- benzoic acid, 1,10-phenanthroline and cobalt perchlorate anhydrous has been synthesized in the solvent mixture of water/methanol and characterized. Crystal data for this complex: tetragonal, space group I41, a = 2.0356(2), c = 1.3779(3) nm, V = 5.7096(15) nm3, Mr = 581.51, μ(MoKα) = 0.644, Dc = 1.353 g/cm3, Z = 8, F(000) = 2424, final S = 1.005, R = 0.0404 and wR = 0.0865. The crystal structure shows that the cobalt ion is coordinated with two nitrogen atoms of one 1,10-phenanthroline molecule, three oxygen atoms from three 2,4,6-trimethylbenzoic acid mole- cules and one water molecule, giving a distorted octahedral coordination geometry. The result of TG analysis indicates that the title complex is stable till 200 ℃.     

Synthesis and Crystal Structure of 4,6-Di-tert-butyl-2-hydroxy-3-(N-1-phenylethyliminomethyl)phenyl bis(triphenylphosphine)palladium bromide

１ＩＮＴＲＯＤＵＣＴＩＯＮＰａｌａｄｉｕｍｃｏｍｐｌｅｘｅｓｓｕｃｈａｓｔｅｔｒａｋｉｓ（ｔｒｉｐｈｅｎｙｌｐｈｏｓｐｈｉｎｅ）ｐａｌａｄｉｕｍａｒｅａｋｉｎｄｏｆｉｍｐｏｒｔａｎｔｃａｔａｌｙｓｔｓｉｎｔｈｅｒｅａｃｔｉｏｎｏｆｃａｒｂｏｎ ｃａｒ...     

New volatile complexes of Ni(II) and Pd(II) with 2,2,6,6-tetramethyl-3-amino-4-hepten-5-one: Structure and properties

New volatile β-iminoketonate complexes of Ni(L)₂ and Pd(L)₂ were obtained. β-Aminovinylketone C(CH₃)₃C(NH₂)CHC(O)C(CH₃)₃ was used as HL. Synthesis of the compound is described, and element analysis, DTA, and IR spectral data are given. The complexes were investigated by XRPA and XRD. The structures are molecular, consist of the trans complexes, and are isostructural. The central atoms have a square plane environment with a (MO₂N₂) coordination unit. The M-O and M-N distances and the N-M-O valence chelate angles are equal, 1.834 Å, 1.848 Å, and 94.2° for Ni(L)₂ and 1.972 Å, 1.975 Å, and 92.4° for Pd(L)₂.     

Synthesis and structure of a complex of copper(II) bromide with bis(benzotriazol-1-yl)methane

The preparation technique of a complex of copper(II) bromide with bis(benzotriazol-1-yl)methane (L), (Cu₂L₂Br₄)_n, is developed. The compound is studied by single crystal and powder X-ray diffraction and static magnetic susceptibility techniques. According to single crystal XRD data, the complex has a layered structure determined by bidentate bridging coordination of L with N(3) and N(3′) atoms to copper(II). The elementary unit of {Cu₂(μ-Br)₂Br₂} polymer has a binuclear structure. The coordination polyhedron is a trigonal pyramid, and the coordination core is CuN₂Br₃. The temperature dependence of effective magnetic moment is studied within an interval of 2–300 K. The nature of the μ_eff(T) dependence indicates that antiferromagnetic exchange interactions dominate in exchange clusters of the complex with an even number of paramagnetic centers. Original Russian Text Copyright ? 2007 by E. V. Lider, A. S. Potapov, E. V. Peresypkina, A. I. Smolentsev, V. N. Ikorskii, A. I. Khlebnikov, and L. G. Lavrenova __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 48, No.3, pp.543–547, May–June, 2007.     

Reaction of 3-Aryl-1-(2-methyloxiran-2-yl)prop-2-en-1-ones with Tosylhydrazine

It was established that the reaction of 3-aryl-1-(2-methyloxiran-2-yl)prop-2-en-1-ones with tosylhydrazine leads to 3-[(E)-2-arylvinyl]-4-methyl-1-tosyl-1H-pyrazoles and 3-aryl-1-(2-methyloxiran-2-yl)-3-tosylpropan-1-ones. The latter are formed as a result of rearrangement of the intermediate hydrazino alcohols and/or addition of p-toluenesulfinic acid during reductive degradation of the tosylhydrazine. It was shown that the reaction of 3-aryl-1-(2-methyloxiran-2-yl)-3-tosylpropan-1-ones with an excess of tosylhydrazine leads to 3-(2-aryl-2-tosylethyl)-4-methyl-1-tosyl-1H-pyrazoles. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1481–1489, October, 2005.     

双环[2.2.1]-2-庚烯-5，6-二甲酸镍配合物的合成、晶体结构及热稳定性

The nickel complex Ni(phen)(H₂O)₃[C₈H₁₁O₂(COO)] has been synthesized with bicycle[2.2.1]hept-2-en-5,6-dicarboxylic acid [C₇H₈(COOH)₂] by means of solvent way. It crystallizes in the triclinic space group P1, with a=0.780 58(16) nm, b=1.189 9(2) nm, c=1.214 8(2) nm, α=66.20(3)°, β=88.28(3)°, γ=86.33(3)°, V=1.030 3(4) nm³, D_c=1.554 g·cm^-3, Z=2, F(000)=502. Final GOF=1.107, R₁=0.026 4, wR₂=0.070 2. The crystal structure shows that the nickel ion is coordinated with four oxygen atoms from one bicycle[2.2.1]-2-hepten-5,6-dicarboxylic acid molecule and three water molecules, respectively, with two nitrogen atoms from the 1,10-phenanthroline molecule, forming a distorted octahedral coordination geometry. The result of TG analysis shows that the title complex was stable under 210.0 ℃. CCDC: 741933.     

Ternary inclusion complexes of cyclodextrins with spin-labeled indoles and hydrocarbons. The formation of 2: 1: 2 complexes and partial dissociation of spin-labeled guests in the presence of a hydrocarbon liquid phase

The interaction of ternary complexes γ-or β-cyclodextrin (CD)-spin-labeled indole (pyrrolidine (1) or piperidine (2) derivative)-hydrocarbon (benzene or cyclohexane) with the liquid phase of these hydrocarbons gives rise to a new type of complexes (s) the ESR spectra of which are indicative of a much lower rotational mobility and its weaker temperature dependence for the spin-labeled guests compared with the initial ternary complexes (w). The formation of s-complexes is accompanied by a decrease in the proportion of the initial w-complexes. This gives rise to several isosbestic points in the ESR spectra, which indicates the formation of s-complexes from w-complexes. The rotational diffusion coefficient of 2 in s-complexes decreases 6–10-fold with respect to its value for w-complexes and the libration amplitude of 1 in the s-complexes decreases to 5–6° at 295 K. Transition between the two types of complexes occurs with characteristic times of 10³–10⁵ s and is reversible: upon the removal of the hydrocarbon, the proportion of the strongly immobilized s-signal decreases, while upon its addition, it increases again. These results indicate that the strongly immobilized ESR signals belong to 2: 1: 2 complexes, which are formed upon the insertion of the second hydrocarbon molecule into the initial ternary 2: 1: 1 w-complexes. According to PM3 quantum-chemical calculations, 2: 1: 2 complexes are stable in energy and the geometry of hydrocarbon arrangement depends on the structure of the spin-labeled guest. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2094–2100, December, 2006.     

Crystal and molecular structure of <Emphasis Type="Italic">tris</Emphasis>-(1,1,1-trifluoro-5,5-dimethylhexan-2,4-dionato)iron(III)

Synthesis and results of the single crystal X-ray diffraction study of iron(III) pivaloyltrifluoroacetonate are reported. Crystal data for C₂₄H₃₀FeF₉O₆: a = 9.2205(6) Å, b = 9.6584(10) Å, c = 17.3799(17) Å, α = 75.902(2)°, β = 80.517(3)°, γ = 82.746(3)°, space group P-1, V = 1474.6(2) ų, Z = 2. The structure is molecular with the octahedral environment of Fe atom, Fe-O_av 1.991 Å, ∠O-Fe-O_av 86.48°. The van der Waals energy of intermolecular interactions is calculated and compared to thermodynamic data.     

Synthesis and Crystal Structure of Bis(nitrate)bis(dipiperidin-1-yl-methanone)uranyl(II)

1 INTRODUCTION The extraction chemistry of uranium is a veryimportant research field, and the new high extrac-tants of uranium have being studied for several deca-des[1, . Our interest is studying the behaviors of new 2]extractants and their st…