配合物[Cu(PTA)(phen)2]·(PTA)·(H2O)4的合成、晶体结构及电化学性质

The title complex has been synthesized by using terephthalic acid (PTA), 1,10-phenanthroline (phen) and copper monohydrate. It crystallizes in monoclinic space group C2/c with a=2.959 0(2) nm, b=1.466 4(10) nm, c=1.764 3(12) nm, β=105.593(11)°, V=7.372(9) nm³, Dc=1.489 g·cm^-3, Z=8, F(000)=3 416, R₁=0.043 6, wR₂= 0.151 9. The crystal structure shows that the copper atom is coordinated with four nitrogen atoms from two phens and one oxygen atom from one terephthalic acid, forming a distorted square-pyramid coordination geometry. The cyclic voltametric behavior of the complex is also reported. CCDC: 277047.     

混合配体配合物[Cd2(phen)4(bmal)2]·3H2O的合成与晶体结构研究

A novel binucleus mixed-ligand[Cd₂(phen)₄(bmal)₂]·3H₂O (phen=phenanthroline; bmal=benzylmalonic acid radical) has been synthesized by the reaction of phen and bmal with cadmium(Ⅱ) salt. X-ray crystal structure analysis was carried out to determine the crystal structure of the title complex. The crystal of the title complex belongs to monoclinic system with space group P2₁/c, a=1.119 1(8) nm, b=2.480 5(17) nm, c=1.063 4(8) nm, β=142.042(12)°, Z=4, V=2.887(3) nm³, D_c=1.613 g·cm^-3, R₁=0.046 2, wR₂=0.115 6, F(000)=1 424. One carboxyl of bmal is coordinated to Cd(1) with monodentate form, the others are coordinated to Cd(2) with bidentate form. The complexes form a 1-D chain structure bridged by hydrogen bonds that formed by uncoordinated water and oxygen atom of carboxyl group in bmal, the 2-D network structure was formed by π-π interaction of neighbouring phen. CCDC: 257080.     

四元混配配合物[Ce(CH2=C(CH3)-COO)2(NO3)(phen)]2的合成、表征及晶体结构

A new complex with mixed-quadriligand [Ce(CH₂=C(CH₃)-COO)₂(NO₃)(phen)]₂ has been synthesized in aqueous solution of slight acidity and characterized by elementary analysis, IR and TGA. The crystal structure determination shows that the complex belongs to triclinic, space group P1, a=9.614?, b=10.047?, c=11.821?, Z=2, α=100.88(3)°, β=106.29(3)°, γ=97.93(2)°, V=1054(5)?³, D_c=1.741g·cm^-3, F(000)=546.00, μ(MoKα)=22.06cm^-1. And the crystal is consisted of a binuclear molecule. The coordina-tion of Ce³⁺ is nine.     

[Ce(NO3)5H2O]·(C3H5N2)2的合成、晶体结构及热分析

Colorless crystal, [Ce(NO₃)₅H₂O]·(C₃N₂H₅)₂, has been obtained from the reaction of Ce(NO₃)₃ with imdazole in the aqueous solution and its crystal structure has been determined by single crystal X-ray diffraction techniques.The crystal belongs to triclinic, space group P1. The cell parameters are: a = 0.7489(1) um, b = 0.7914(2) nm, c = 1.8139(3) nm, a = 89.39(2)°, β = 89.37(l) °,γ = 63.18(2)°, Dc = 2.1g·cm^-3, Z = 2, R = 0.0319.In the compound, all of five nitrates are bidentate and one molecule of water is monodentate, the coordination number of Ce (Ⅲ) is 11.The processes of thermal decomposition of the compound was proposed by its TGcurve.     

配合物[Cu2(phen)2](SiW12O40)(H2O)7的合成、晶体结构及电化学分析

The title complex has been synthesized by the reaction of silicotungstic acid, 1,10-phenanthroline (phen) monohydrate and cupric acetate. The crystal structure belongs to triclinic system, space group P1 with a=1.158 46(15) nm, b=1.658 8(2) nm, c=1.664 4(2) nm, α=82.090(2)°, β=76.001(2)°, γ=86.531(2)°, and V=3.072 6(7) nm³, D_c=3.887 g·cm^-3, Z=2, F(000)=3 196. R₁=0.086 7, wR₂=0.185 8. The structure shows that the copper(Ⅱ) atom is coordinated with two nitrogen atoms from the one phen and three oxgygen atoms from three water, forming a distorted square-pyramid configuration The cyclic voltametric behavior of the complex is also reported. CCDC: 298807.     

配合物[Ni(phen)3][(C6H5)2C(OH)COO]2·6H2O的合成、晶体结构及电化学性质

The title complex with benzilic acid and 1,10-phenanthroline monohydrate has been synthesized and characterized in the solvent mixture of water and methyl-alcohol. It falls into the triclinic, characteristic of the space group P1 with a=1.142 8(3) nm, b=1.638 8(4) nm, c=1.645 6(4) nm, α=74.428(5)°, β=84.205(5)°, γ=74.917(5)°, V=2.864 9(12) nm³, D_c=1.347 g·cm^-3. Z=2, F(000)=1 216, the reliability factor R₁=0.068 9, wR₂=0.189 9. The crystal structure shows that the nickel atom is coordinated with six nitrogen atoms from the three phens, forming a distorted octahedral coordination geometry. The cyclic voltametric behavior of the complex is also reported. CCDC: 274184.     

[Mn(NH2NHCO2C2H5)3](NO3)2的晶体结构和热分解机理

[Mn(ECZ)₃](NO₃)₂ is newly prepared by the aqueous solutions of Mn(NO₃)₂ and ethyl carbazate (ECZ). The crystal structure has been determined by X-ray crystal diffraction analysis. It belongs to monoclinic with space group of P2₁/n. The crystal parameters are: a=1.3974(2) nm, b=0.8796(2) nm, c=3.4322(7) nm, β=91.25(1) °, V= 4.2175(1) nm³, Z=8. Its molecular weight is 491.30. Mn²⁺ is located on the center of the molecular structure. Ethyl carbazate serves as a bidentate ligand which coordinates to the metal cations with its carbonyl oxygen atom and the terminal hydrazine nitrogen atom, forming five-member chelating rings, and three such rings are formed in each molecule. The coordination number of the metal ion is six and the coordination configuration of the central ion is octahedral. Specially, antimer configuration phenomenon is found in the molecule. The complex is further characterized by element analysis and IR measurements. The thermal decomposition mechanism is studied by using TG-DTG and DSC techniques. CCDC: 215675.     

铋(Ⅲ)四氢吡咯氨荒酸配合物[Bi(S2CNC4H8)3]2的合成和晶体结构

The novel bismuth(Ⅲ) complex with dithiotetrahydropyrrolocarbamate, [Bi(S₂CNC₄H₈)₃]₂ has been synthe-sized. The crystal structure has been determined by X-ray single crystal diffraction. The crystal belongs to mono-clinic with space group C2/c, a=1.6356(9) nm, b=1.1875(6) nm, c=2.3954(13) nm, β=100.741(8)°, Z=4, V=4.571(4) nm³, D_x=1.882g·cm^-3,μ=8.267mm^-1, F(000)=2512, R=0.0404, wR=0.0622. In this binuclear complex, each Bi(Ⅲ) is seven coordinate with a distorted pentagonal bipyramidal geometry. CCDC: 179924.     

甲酸桥联四核锰配合物[Mn4(O2CH)4(phen)8](ClO4)4·6H2O的水热合成和晶体结构

The title compound, [Mn₄(O₂CH)₄(phen)₈](ClO₄)₄·6H₂O(1), where phen=1,10-phenanthroline, was synthes-ized and its crystal structure was determined by X-ray diffraction structure analysis. The crystal is of monoclinic, space group P2/c with a=1.928 0(16) nm, b=1.297 0(11) nm, c=2.126 4(18) nm, V=5.242 2(8) nm³, Z=2, M_r=2 347.36, D_c=1.487 g·cm^-3, μ=0.659 mm^-1, F(000)=2 400, R_int=0.043 7, R=0.052 3, wR=0.118 6. The Mn atoms are octahed-rally coordinated by two O atoms of two ligands and four N atoms of two 1,10-phenanthroline molecules. The carboxyl group coordinates to Mn(Ⅱ) in the bridging bidentate mode. CCDC: 675520.     

配合物[Mn(bipy)3](ClO4)2的晶体结构和热分析研究

The complex [Mn(bipy)₃]·(ClO₄)₂ was synthesied and characterized by X-ray diffraction. X-ray diffraction result for the single crystal showed that the crystal belongs to triclinic, space group P1, a=0.8123(2),b=1.1024(2), c=1.8646(4)nm,α=102.30(3)°,β=91.00(3)°,γ=99.69(3)°,V=1.6056(6)nm³,Z=2,D_c=1.494g·cm^-3. The thermal decomposition of [Mn(bipy)₃](ClO₄)₂ occurred in a three steps pattern. The reaction mechanism of the first step decomposition was deduced as n(1-α)[-ln(1-α)](n-1)/n with the activation energy of 130kJ·mol^-1.     

Structure of two new borates YCa3(AlO)3(BO3)4 and YCa3(GaO)3(BO3)4

By replacing Mn in YCa₃(MnO)₃(BO₃)₄ with trivalent Al and Ga, two new borates with the compositions of YCa₃(MO)₃(BO₃)₄ (M=Al, Ga) were prepared by solid-state reaction. Structure refinements from X-ray powder diffraction data revealed that both of them are isostructural to gaudefroyite with a hexagonal space group P6₃/m. Cell parameters of a=10.38775(13)Å, c=5.69198(10)Å for the Al-containing compound and a=10.5167(3)Å, c=5.8146(2)Å for the Ga analog were obtained from the refinements. The structure is constituted of AlO₆ or GaO₆ octahedral chains interconnected by BO₃ groups in the ab plane to form a Kagomé-type lattice, leaving trigonal and apatite-like tunnels. It is found that most rare-earth and Cr, Mn ions can be substituted into the Y³⁺ and M³⁺ sites, respectively, and the preference of rare-earth ions to locate in the trigonal tunnel is correlated to the sizes of the M³⁺ ions.     

Synthesis and characterisation of HRuRh3(CO)12. Crystal structures of HRuRh3(CO)12, HRuRh3(CO)10(PPh3)2 and HRuCo3(CO)10(PPh3)2

A new ruthenium-rhodium mixed-metal cluster HRuRh₃(CO)₁₂ and its derivatives HRuRh₃(CO)₁₀(PPh₃)₂ and HRuCo₃(CO)₁₀(PPh₃)₂ have been synthesized and characterized. The following crystal and molecular structures are reported: HRuRh₃(CO)₁₂: monoclinic, space group P2₁/c, a 9.230(4), b 11.790(5), c 17.124(9) Å, β 91.29(4)°, Z = 4; HRuRh₃(CO)₁₀(PPh₃)₂·C₆H₁₄: triclinic, space group P$\text{1}$, a 11.777(2), b 14.079(2), c 17.010(2) Å, α 86.99(1), β 76.91(1), γ 72.49(1)°, Z = 2; HRuCo₃(CO)₁₀(PPh₃)₂·CH₂Cl₂: triclinic, space group P$\text{1}$, a 11.577(7), b 13.729(7), c 16.777(10) Å, α 81.39(4), β 77.84(5), γ 65.56°, Z = 2. The reaction between Rh(CO)₄^? and (Ru(CO)₃Cl₂)₂ tetrahydrofuran followed by acid treatment yields HRuRh₃(CO)₁₂ in high yield. Its structural analysis was complicated by a 80–20% packing disorder. More detailed structural data were obtained from the fully ordered structure of HRuRh₃(CO)₁₀(PPh₃)₂, which is closely related to HRuCo₃(CO)₁₀(PPh₃)₂ and HFeCo₃(CO)₁₀(PPh₃)₂. The phosphines are axially coordinated.     

Pd(PBu 3 t ) Adducts of Os3(CO)12. Synthesis and Structures of Pd2Os3(CO)12(PBu 3 t )2 and Pd3Os3(CO)12 (PBu 3 t )3

Two new compounds Pd₂Os₃(CO)₁₂ , 13 and Pd₃Os₃(CO)₁₂ , 14 have been obtained from the reaction of with Os₃(CO)₁₂ at room temperature. The products were formed by the addition of two and three groups to the Os–Os bonds of Os₃(CO)₁₂. Compounds 13 and 14 interconvert between themselves by intermolecular exchange of the groups in solution. Compounds 13 and 14 have been characterized by single crystal X-ray diffraction analyses.Dedicated to Professor Brian F. G. Johnson on the occasion of his retirement – 2005.     

The thermal decomposition reactions of [Co(en)3](NO3)3 and [Co(en)3](HSO4)3

The thermal decomposition reactions were determined for [Co(en)₃](N0₃)₃ and [Co(en)₃(HSO₄)₃ in a dynamic nitrogen gas atmosphere and _vacuo, where en represents ethylenediamine. Data were obtained using thermogravimetry, DTA, thermomagnetic analysis, and mass spectrometry. The dissociation reactions in nitrogen were found to be as follows:

and

In vacuo, the dissociation process for [Co(en)₃](N0₃)₃ is the same as in nitrogen. Also, the decomposition of [Co(en)₃](HSO₄)₃ is the same except for the first step which is:

     

Magnetic investigation of Cu(NH3)4(NO3)2

The magnetic properties of Cu(NH₃)₄(NO₃)₂ have been measured at low temperatures. Broad maxima in both the susceptibility and specific heat are observed and are consistent with linear chain behavior of a Heisenberg antiferromagnet, with J/k = 3.9 ± 0.1 K. Long-range order sets in at T_c = 0.15 ± 0.01 K, and the ratio kT_c/|J| = 0.038 is the lowest observed as yet for a one-dimensional, S = 1/2 antiferromagnet.     

The preparation and X-ray crystal structure of W3(μCN)3(NO)3(CO)9

The nitrosation of Na[W(CO)₅CN] using amyl nitrite and sulphuric acid in a two phase water— diethyl ether system gives the trinuclear compound W₃(μCN)₃(NO)₃(CO)₉. A single crystal X-ray diffraction study showed that the compound contains a nine-membered ring of three tungsten atoms and three bridging cyanide groups. The terminal carbonyl and nitrosyl ligands were not distinguishable.     

Conductivities of the Ternary Systems Y(NO3)3+La(NO3)3+H2O, La(NO3)3+Ce(NO3)3+H2O, La(NO3)3+Nd(NO3)3+H2O and Their Binary Subsystems at Different Temperatures

Electrical conductivities were measured for the ternary systems Y(NO₃)₃+La(NO₃)₃+H₂O, La(NO₃)₃+Ce(NO₃)₃+H₂O, La(NO₃)₃+Nd(NO₃)₃+H₂O, and their binary subsystems Y(NO₃)₃+H₂O, La(NO₃)₃+H₂O, Ce(NO₃)₃+H₂O, and Nd(NO₃)₃+H₂O at (293.15, 298.15 and 308.15) K. The measured conductivities were used to test the generalized Young’s rule and the semi-ideal solution theory. The comparison results show that the generalized Young’s rule and the semi-ideal solution theory can yield good predictions for the conductivities of the ternary electrolyte solutions, implying that the conductivities of aqueous solutions of (1:3 + 1:3) electrolyte mixtures can be well predicted from those of their constituent binary solutions by the simple equations.     

Anion effect on the thermolysis of double complexes [Co(NH3)6][Fe(CN)6] and [Co(NH3)6]4[Fe(CN)6]3

The thermolysis of complexes [Co(NH₃)₆][Fe(CN)₆] and [Co(NH_{3 6}]₄[Fe(CN)₆]₃ under an air or hydrogen atmosphere at 200, 350, and 500°C is studied. The composition and properties of thermolysis products are determined. The oxidative thermolysis yields mixtures of oxides of the central metals; the reductive thermolysis yields intermetallic compounds CoFe. The density of the complexes and the specific surface area of the intermetallic compounds are measured. Average particle sizes are calculated. The morphology and dispersion of the powders are dictated by the shape and density of the crystals of the precursor double salts and the thermolysis temperature. The thermolysis chemism in the oxidative and reductive atmospheres is discussed in the context of the nature of the complex anion. Original Russian Text ? S.I. Pechenyuk, D.P. Domonov, D.L. Rogachev, A.T. Belyavskii, 2007, published in Zhurnal Neorganicheskoi Khimii, 2007, Vol. 52, No. 7, pp. 1110–1115.     

The molecular structures of H2Os3(CO)10, H(SC2H5)Os3(CO)10 and (OCH3)2Os3(CO)10

X-ray crystallographic analyses of H₂Os₃(CO)₁₀, H(SC₂H₅)Os₃(CO)₁₀ and (OCH₃)₂Os₃(CO)₁₀ are reported. Although hydrogen atom positions have not been located, the essential isostructural nature of the three commplexes establishes the hydride ligands as bridging two metal atoms, separated by 2.670 Å, with a formal bond order of two; the bridging hydrido- and thiolato-ligands span an osmium---osmium bond of length 2.863 Å and formal bond order one; the two μ-methoxy ligands bridge two metal atoms separated by 3.078 Å which, by simple 18 electron rule counting, has a metal---metal bond order of zero. Some general comments are made on the structures of polynuclear transition metal carbonyls.     

Ba3 (VO4)2-K2 Ba(MoO4)2 and Pb3 (VO4)2-K2 Pb(MoO4)2 systems

Phase equilibria in the Ba₃(VO₄)₂-K₂Ba(MoO₄)₂ and Pb3(VO₄)₂-K₂Pb(MoO₄)₂ systems have been investigated. In the first system, a continuous series of substitutional solid solutions with the palmierite structure is formed, and in the second one, the polymorphic transition in lead orthovanadate at 100°C restricts the extent of the palmierite-type solid solution to 10–100 mol % K₂Pb(MoO₄)₂. Original Russian Text ? V.D. Zhuravlev, Yu.A. Velikodnyi, A.S. Vinogradova-Zhabrova, A.P. Tyutyunnik, V.G. Zubkov, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 10, pp. 1746–1748.