Critical temperatures,pressures, and densities for the mixtures CO2–C3H8, CO2–nC4H10, C2H6–C3H8, and C3H8–nC4H10

A simple method is developed to estimate mixture critical temperatures (T_c), pressures (P_c), and densities (ρ_c) as a function of overall composition (X) from near critical region experimental coexistence data. This three-step method is applied to four mixtures, CO₂–C₃H₈, CO₂–nC₄H₁₀, C₂H₆–C₃H₈, and C₃H₈–nC₄H₁₀. Isothermal liquid–vapor coexistence data, which includes temperature, vapor pressure, coexisting densities (ρ^ℓ and ρ^v), and coexisting compositions for the more volatile component (x₁^v and x₁^ℓ) are used. In the first step, the difference of the saturated liquid and vapor densities (ρ^ℓ−ρ^v) is fitted to an empirical function in ((P_c−P)/P_c) to obtain P_c. Then P/P_c and ((ρ^ℓ+ρ^v)/2ρ_c) are simultaneously fitted to functions of a polynomial in (X₁−(x₁^v+x₁^ℓ)/2) yielding estimates of ρ_c and X₁. Finally, the discrete estimated critical data points are fitted with an equation to provide a continuous representation of the critical lines. The method is successfully tested for the mixtures, CO₂–C₃H₈ and CO₂–nC₄H₁₀, for which there is a reasonable amount of isothermal data. The procedure is then applied to the mixtures, C₂H₆–C₃H₈ and C₃H₈–nC₄H₁₀, for which there are sparse data. For all four mixtures, the critical temperature line, T_c vs. X₁, matches literature values within ±0.5%. The critical pressure line, P_c vs. X₁, and critical density line, ρ_c vs. X₁, match literature values, in general, within ±2%.     

Synthesis,Spectroscopic Properties and Crystal Structure of (C4N2H12)2Zr(C2O4)4·H2O

The title compound (C4N2H12)2Zr(C2O4)4·H2O 1 was synthesized by the reaction of ZrOCl2·8H2O, H2C2O4·2H2O and piperazinium in aqueous solution. Single-crystal X-ray analysis has revealed that compound 1 (C16H26N4O17Zr, Mr = 637.63) crystallizes in the monoclinic system, space group P21/c with a = 9.0425(3), b = 13.3844(3), c = 19.1191(5)A, β = 98.365(1)o, V = 2289.34(11) A3, Z = 4, Dc = 1.850 g/cm3, F(000) = 1304, μ = 0.577 mm-1, the final R = 0.0240 and wR = 0.0628 for 4386 observed reflections with I > 2σ(I). X-ray crystal-structure analysis suggests that compound 1 consists of [Zr(C2O4)4]4- anion and two protonated piperazinium cations. The anions are linked through hydrogen bonds of piperazinium. FT-IR and Raman spectra clearly show the existence of oxalate groups in the crystal lattice.     

Synthesis and characterisation of MIL-43 and MIL-44, two new layered templated tetravalent phosphates: Zr(PO4)2·N2C2H10 and Ti2(PO4)2(HPO4)2·N2C2H10

Zr(PO₄)₂·N₂C₂H₁₀ or MIL-43 and Ti₂(PO₄)₂(HPO₄)₂·N₂C₂H₁₀ or MIL-44 were prepared hydrothermally (20 or 4 days, 473 or 453 K, respectively, autogenous pressure) in the presence of ethylenediamine. Their structures have been determined by single-crystal X-ray diffraction. MIL-43 crystallises in the monoclinic space group P2₁ (No. 4) with a=11.0722(1), b=10.6631(1), c=16.4642(2) Å, β=95.991(1)° and V=1933.21(3) Å³ (final agreement factors R₁(F)=0.0466, wR₂(F²)=0.1096). Due to the very poor quality of the crystal, only an approached structure of MIL-44 is given; it crystallises in the triclinic space group P1 (No. 1) with a=5.0845(4), b=6.3097(5), c=12.6111(9) Å, α=77.454(1), β=78.926(2), γ=89.986(1)° and V=387.21(5) Å³. Both solids are two-dimensional and are the ion-exchanged equivalents of the layered solids αZrP and γTiP. Inorganic sheets of MIL-43 are built up from pseudo-hexagonal arrays of ZrO₆ octahedra surrounded by PO₄ tetrahedra pointing their terminal oxygen alternatively up and down at the interlayer space. Layers of MIL-44 are made of double (TiOP) chains built from TiO₆ octahedra and PO₄ tetrahedra on which HPO₄ groups are grafted pointing towards the interlayer space. In both cases, diprotonated organic templates, located between the layers, interact with terminal phosphate groups and ensure via hydrogen bonds the stability of the structures.     

The mechanism and kinetics of energy transfer processes in the Xe–CCl4–M (M=CH4, C2H2, C2H4, C2H6 C3H6 and C3H8) mixtures irradiated by xenon resonance light

The mechanism and kinetics of energy transfer from Xe(6s[3/2]₁) resonance state (E=8.44 eV) to selected hydrocarbon molecules have been investigated by XeCl(B–X) (λ_max=308 nm) fluorescence intensity measurements at stationary conditions in Xe–CCl₄–M systems. Steady-state analysis of the fluorescence intensity dependence on the xenon and M pressure at constant CCl₄ concentration shows that these process occur in the two- and three-body reactions: Xe(6s[3/2]₁⁰)+M→products, Xe(6s[3/2]₁⁰+M+Xe→products. The two- and three-body rate constants for these reactions have been found (see Table 1Table 1. Experimental parameters of Eq. (8)found by least square method in Xe–CCl₄–C₂H₂ and Xe–CCl₄–C₂H₄ systems for chosen xenon pressures in the range 25–150 Torr. Linear correlation coefficients (R) are also shown     

5.

New 1D and 2D metal oxygen connectivities in Cu(II) succinato and glutarato coordination polymers: [Cu3(H2O)2(OH)2(C4H4O4)2] · 4H2O, [Cu4(H2O)2(OH)4(C4H4O4)2] · 5H2O and [Cu5(OH)6(C5H6O4)2] · 4H2O     

《Journal of Coordination Chemistry》2012,65(21):3420-3437

Two Cu(II) hydroxo succinates [Cu₃(H₂O)₂(OH)₂(C₄H₄O₄)₂]?·?4H₂O (1) and [Cu₄(H₂O)₂(OH)₄(C₄H₄O₄)₂]?·?5H₂O (2) and one Cu(II) hydroxo glutarate [Cu₅(OH)₆(C₅H₆O₄)₂]?·?4H₂O (3) have been prepared and structurally characterized by single crystal X-ray diffraction methods. They feature 1D and 2D copper oxygen connectivity of elongated {CuO₆} octahedra in “4?+?1?+?1” and “4?+?2” coordination geometries. Within 1, linear trimers of three edge-sharing {CuO₆} octahedra are connected into copper oxygen chains, which are bridged by the anti conformational succinate anions to generate 2D layers with mono terminally coordinating gauche succinate anions on both sides. The layers are assembled into a 3D framework by interlayer hydrogen bonds with lattice H₂O molecules distributed in channels. Different from 1, the principal building units in 2 are linear tetramers of four edge-sharing {CuO₆} octahedra. The tetramers are condensed into copper oxygen chains and the succinate anions interlink them into a 3D framework with triangular channels filled by lattice H₂O molecules. The {CuO₆} octahedra in 3 are edge-shared to form unprecedented 2D inorganic layers with mono terminally coordinating glutarate anions on both sides. Interlayer hydrogen bonding interactions are responsible for supramolecular assembly of the layers into a 3D framework with lattice H₂O molecules in the channels. The inorganic layers in 3 can be described as hexagonal close packing of oxygen atoms with the Cu atoms in the octahedral cavities. The title compounds were further characterized by elemental analyses, IR spectra and thermal analyses.     

6.

Synthesis and crystal structure of [Zn(H2O)4(C4H2O4)]·H2O     

《Journal of Coordination Chemistry》2012,65(15):1291-1297

     

7.

Reactions of SiH2(X̄1A1) with H2, CH4, C2H4, SiH4 and Si2H6 at 298 K     

《Chemical physics letters》1985,122(4):361-364

Reaction rate constants of SiH₂(X̄¹A₁) have been directly measured for the first time using the laser photolysis—laser-induced fluorescence method. The preparation of SiH₂ radical in the laser photolysis (193 nm) of phenylsilane and the concentration of the radical is demonstrated by a dye laser at 580.1 nm (X̄¹A₁-Ā¹B₁). The reaction rate constants of SiH₂(X̄¹A₁) with H₂, CH₄, C₂H₄, SiH₄ and Si₂H₆, are 0.001, 0.01, 0.97, 1.1 and 5.7×10⁻¹⁰ cm³ molecule⁻¹ s⁻¹, respectively. For SiH₂(Ā¹B₁(0.2,0)), the collision-free lifetime is 0.6 μs and the quenching rate constant for He is 3.8×10⁻¹⁰ cm³ molecule⁻¹ s⁻¹.     

8.

Syntheses and crystal structures of two Cd(II) coordination polymers: one-dimensional chain [Cd(C4H6N2)2(C4H2O4)(H2O)2] n and two-dimensional sheet [Cd(C4H6N2)(H2O)(C4H4O4)] n  ·  n H2O     

《Journal of Coordination Chemistry》2012,65(24):2679-2686

Two new Cd(II) coordination polymers, [Cd(C₄H₆N₂)₂(C₄H₂O₄)(H₂O)₂] _n (1) (where C₄H₆N₂?=?2-methylimidazole, C₄H₂O₄?=?fumarate), and [Cd(C₄H₆N₂)(H₂O)(C₄H₄O₄)] _n ?·?nH₂O (2), (where C₄H₄O₄?=?succinates), have been prepared and structurally characterized by single crystal X-ray diffraction. Complex 1 crystallizes in the triclinic space group P 1 in a one-dimensional chain structure, in which carboxy is monodentate; a three-dimensional supermolecular network structure was formed through hydrogen bonding. In complex 2, the coordination geometry of the Cd atoms is a pentagonal bipyramid, and a two-dimensional sheet is formed though carboxyl group bridging. In 1 and 2, IR spectra indicate the presence of bridging carboxyl groups, confirmed by structure analyses.     

9.

Synthesis, IR spectra, and solid-state luminescence of triphenylguanidinium salts with the anions B10H 10 2− , B12H 12 2− , B9C2H 12 2− , [Co(C2B9H11)2]−, and [Ni(C2B9H11)2]−     

E. A. Il’inchik  M. K. Drozdova  O. P. Yur’eva  K. G. Myakishev  V. V. Volkov 《Russian Journal of Inorganic Chemistry》2009,54(12):1866-1871

Triphenylguanidinium Ph₃GH⁺ salts with the anions B₁₀H ₁₀ ^2? , B₁₂H ₁₂ ^2? , B₉C₂H ₁₂ ^2? , [Co(C₂B₉H₁₁)₂]^?, and [Ni(C₂B₉H₁₁)₂]^? were synthesized and described by DTA, IR spectroscopy, and solid-state luminescence. By IR spectroscopy, it was shown that intermolecular interactions involving the NH groups of the cation are enhanced in the sequence [Co(C₂B₉H₁₁)₂]^? ～ [Ni(C₂B₉H₁₁)₂]^? < B₉C₂H ₁₂ ^2? < B₁₂H ₁₂ ^2? < B₁₀H ₁₀ ^2? .     

10.

Syntheses and Structures of Two New Coordination Polymers:[Cu(C14H9O4)(C14H10O4)(C12H12N2)2] and [Ag(C14H9O4)(C13H14N2)]·0.5 H2O     

傅志勇  胡胜民  杜文新  张建军  项生昌  吴新涛 《结构化学》2004,23(2)

Under hydrothermal conditions, two new ribbon-like structures, [Cu(C14H9O4)-analysis revealed that these structures were constructed by mixed ligands. The coordination polymer forms the basic architecture while the weak interactions extend the framework into a secondary structure. The whole structures of them are governed by collaboration of the strong and weak interactions. Compound 1 crystallizes in monoclinic, space group C2/c with a = 17.0485(3), b =1 1.0558(3), c = 22.7623(4) A, β = 102.465(1)°, V = 4189.2(2) A3, Z = 4, Mr = 915.44, Dc = 1.451g/mL, F(000) = 1900 andμ(MoKα) = 0.587 cm-1. The final R and wR are 0.0030 and 0.1022,respectively for 3037 observed reflections with I ＞ 2σ(I). Compound 2 crystallizes in monoclinic,space group P21/c with a = 11.5963(4), b = 11.7004(5), c = 17.1254(5) A,β = 95.620(1)°, V =2312.4(1) A3, Z = 4, Mr = 556.35, Dc = 1.598 g/mL, F(000) = 1132 andμ(MoKα) = 0.912 cm-1The final R and wR are 0.0431 and 0.1050, respectively for 2629 observed reflections with I ＞ 2σ(I).     

11.

Synthesis, crystal structure, and thermal stability of [Mo2O4(μ2-O)(C6H4O2)2(H2O)] · (C8H9N2)2 · 2H2O     

X. J. Xu 《Russian Journal of Coordination Chemistry》2014,40(1):48-53

From hydrothermal treatment of benzene-1,2-diamine, pyrocatechol, and MoO₃ in acetic acid solution, a new compound, [Mo₂(μ₂-O)₂(C₆H₄O₂)₂(H₂O)] · (C₈H₉N₂)₂ · 2H₂O (I), constructed from pyrocatechol chelated dinuclear molybdenum units and 2-methylbenzimidazole has been synthesized. Single-crystal structure analysis reveals that the compound crystallizes in the monoclinic space group P2₁/c with a = 23.365(2), b = 7.2214(5), c = 19.3021(16) β = 97.929(4), V = 3225.6(5), Z = 4, M = 808.46, ρ_c = 1.665 g/cm³, μ(MoK _α) = 0.84 mm^?1, F(000) = 1608, the final R = 0.0622 and wR = 0.1484 for 7385 independent reflections with R _int = 0.0393. Interestingly, an in situ condensation between acetic acid and benzene-1,2-diamine has occurred, and the unexpected 2-methyl-1-H-benzo[d] imidazoles serve as counterions and N-H donors to form stable hydrogen-bond network in the crystal. Furthermore, intermolecular hydrogen bonds are found among the cations, anions and crystalline water molecules. The double nuclear molybdenum units are connected by O-H...O hydrogen bonds with the crystalline water molecules to form one-dimensional chains, and the chains are further joined together by N-H...O to form a quasi-two dimensional structure.     

12.

CRYSTAL AND MOLECULAR STRUCTURE OF ο-(2-CYANOETHYL)-p- BROMOBENZOYL-FERROCENE OXIME, CsHsFeC5H4C(C5H4Br)NOC2H4CN     

《结构化学》1985,(3)

<正> INTRODUCTION. Since some derivatives of alkylating ferrocene were found to be effective catalysts for promoting combustion speed of high energy fuels, research works on ferrocene derivatives have been rapidly developed.     

13.

Synthesis and structure of the organoantimony peroxide solvates [Sb4(μ2-O)4(O2)2(C6H3MeO-2,Br-5)8]·1.5C4H8O2 and [Sb4(μ2-O)4(O2)2(C6H3MeO-2,Br-5)8]·6C4H8O2     

V. V. Sharutin  O. K. Sharutina  O. V. Chagarova  O. V. Molokova 《Russian Journal of General Chemistry》2011,81(11):2246-2251

The organoantimony peroxide (Ar₂SbO)₄(O₂)₂ (Ar = C₆H₃OMe-2, Br-5) was synthesized by the oxidation of Ar3Sb with hydrogen peroxide in the presence or acetoxime or acetophenone oxime in dioxane. The product crystallizes with various content of the solvent molecules in the crystal unit cell [1.5 (I) and 6 (II), respectively]. An X-ray diffraction analysis of the solvates was performed. Four antimony atoms in the peroxide are in the octahedral coordination, and are linked through bridging oxygen atoms and two peroxide groups. The distances Sb-C, Sb-O_bridge, Sb-O_peroxide, O-O and Sb...Sb are 2.117–2.122, 1.960–1.972, 2.193–2.235, 1.461, 1.465 and 3.223–3.237 Å in I, and 2.112, 2.119, 1.957, 1,966, 2.204, 2,246, 1,467, and 3.2439 Å in II.     

14.

Tetranuclear bismuth complexes Bi4(O)2(O2CC6H2F3-3,4,5)8 · 2C6H6 and Bi4(O)2(O2CC6H2F3-3,4,5)8 · 2C6H4Me2-1,4: Synthesis and structures     

V. V. Sharutin  I. V. Egorova  O. K. Sharutina  T. K. Ivanenko  N. Yu. Adonin  V. F. Starichenko  M. A. Pushilin  A. V. Gerasimenko 《Russian Journal of Coordination Chemistry》2005,31(1):2-8

X-ray diffraction study of tetranuclear organobismuth complexes Bi₄(O)₂(O₂CC₆H₂F₃-3,4,5)₈ · 2⁶-C₆H₆ and Bi₄(O)₂(O₂CC₆H₂F₃-3,4,5)₈ · 2(C₆H₄Me₂-1,4) revealed four Bi atoms connected through the bridging carboxylate ligands and the O atoms. The coordination sphere of the terminal Bi atoms includes the chelate carboxylate ligand and the 6-arene molecule. The bridging O atoms are tricoordinated, the distances between the terminal Bi atom and the center of benzene molecule (1,4-dimethylbenzene) are 3.024 Å(3.131 Å).Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 1, 2005, pp. 4–11.Original Russian Text Copyright © 2005 by Sharutin, Egorova, Sharutina, Ivanenko, Adonin, Starichenko, Pushilin, Gerasimenko.     

15.

Synthesis and Crystal Structure of [Ni(H2O)6][Ni(H2O)2(C4H2O4)]·4H2O     

《Journal of Coordination Chemistry》2012,65(11):967-973

Reaction of a freshly prepared Ni(OH)_{2?2 x} (CO₃) _x ·yH₂O with maleic acid in H₂O at room temperature afforded [Ni(H₂O)₆][Ni(H₂O)₂(C₄H₂O₄)]·4H₂O, which consists of [Ni(H₂O)₆]²⁺ cations, [Ni(H₂O)₂(C₄H₂O₄)]^2? anions and lattice H₂O molecules. Ni atoms in cations are octahedrally coordinated and Ni atoms in anions are each octahedrally coordinated by bidentate chelating maleato ligands and two water molecules at trans positions. Cations and anions are interlinked by hydrogen bonds to form 1D chains, which are hexagonally arranged and connected by the lattice water molecules. When heated in a flowing argon stream, the compound decomposes, with complete dehydration being followed by dissociation of nickel maleate into NiO and maleic anhydride.     

16.

An infrared and Raman spectroscopic study of Td-type 4,4′-bipyridylcadmium(II) tetracyanometallate (II) benzene (1/2) clathrates: Cd(C10H8N2)Cd(CN)4 · 2C6H6 and Cd(C10H8N2)Hg(CN)4 · 2C6H6     

Sevgi Bayari  Ziya Kantarci  Sevim Akyüz 《Journal of inclusion phenomena and macrocyclic chemistry》1994,17(3):291-302

Two new benzene clathrates of the form Cd(4,4-bipyridyl)M(CN)₄ · 2C₆H₆, (M=Cd or Hg) have been prepared in powder form. Their spectral data were compared with those of the corresponding host complexes and found to be consistent with the host structure found in Td-type clathrates.     

17.

Synthesis and Crystal Structure of (C6N3H18)2Ti4O4(C2O4)7·4H2O     

张巧珍  张汉辉  黄长沧  王永净  孙瑞卿  陈义平  曹彦宁  郭文军 《结构化学》2004,23(9)

The title compound (C6N3H18)2Ti4O4(C2O4)7(4H2O 1 (C13H22N3O18Ti2, Mr = 604.14) was synthesized by the reaction of Ti(SO4)2, H2C2O4(2H2O and N-(2-ammonioethyl)- piperazinium (AEPP) in aqueous solution. The single-crystal X-ray analysis has revealed that 1 crystallizes in the triclinic system, space group Pī with a = 9.1437(6), b = 11.4991(10), c = 11.6975(8)A, α = 96.2915(18), β = 107.998(3), γ = 104.276(4)°, V = 1110.35(14)A3, Z = 2, Dc = 1.807 g/cm3, F(000) = 618, μ = 0.815 mm－1, the final R = 0.0463 and wR = 0.1264 for 3718 observed reflections with I > 2σ(I). X-ray crystal-structure analysis suggests that compound 1 consists of [Ti4O4(C2O4)7]6－ anion and two protonated N-(2-ammonioethyl)piperazinium cations. The anions are linked into an infinite chain through Ti4O4(C2O4)8 by sharing the oxalates as bridging ligands.     

18.

Syntheses,crystal structures and antibacterial activities of [Cu2(C11H11NO5S)2(H2O)4] · 5H2O and [Ni2(C11H11NO5S)2(H2O)4] · 2H2O     

《Journal of Coordination Chemistry》2012,65(3):427-439

The binuclear complexes [Cu₂L₂(H₂O)₄] · 5H₂O (1) and [Ni₂L₂(H₂O)₄] · 2H₂O (2) (where L = C₁₁H₁₁NO₅S, H ₂ L = 2-[(3-formyl-5-methyl-2-hydroxy-benzylidene)-amino]ethanesulfonic acid) have been synthesized and characterized by IR, elemental analysis and X-ray diffraction. The crystals belong to the monoclinic system, space group P2₁/c. Complex 1: a = 16.8902(12), b = 11.2829(6), c = 17.4249(11) Å; β = 106.709(4)°; S = 1.131; V = 3180.5(3) ų; Z = 4; D _Calcd = 1.729 g cm^?3; F(000) = 1712; μ = 1.554 mm^?1; R ₁ = 0.0519, wR ₂ = 0.1349; complex 2: a = 11.399(2), b = 19.985(3), c = 7.3694(10) Å; β = 108.664(7)°; S = 1.157; V = 1590.6(4) ų; Z = 2; D _Calcd = 1.604 g cm^?3; F(000) = 800; μ = 1.388 mm^?1; R ₁ = 0.1859, wR ₂ = 0.4346. The geometry around each metal(II) center can be described as slightly distorted octahedral. Water-sulfonic clusters and (H₂O)₄ water clusters can be observed for 1 from the crystal packing diagram, while cavity and offset face-to-face π–π stacking can be observed for 2. The complexes have been tested for the antibacterial activities which show antibacterial activities of 1 for β-hemolytic streptococcus, Staphylococcus aureus and Escherichia coli, and the antibacterial activity of 2 only for β-hemolytic streptococcus.     

19.

Two malonato coordination polymers: syntheses and crystal structures of M(H2O)2(C3H2O4) with M=CO and Ni,C3H4O4 = malonic acid     

《Journal of Coordination Chemistry》2012,65(17-18):1537-1543

     

20.

Molar heat capacity and thermodynamic properties of Lu(C5H9NO4)(C3H4N2)6(ClO4)3·5HClO4·10H2O     

X.-C. Lv  Z.-C. Tan  X.-H. Gao  P. Chen 《Journal of Thermal Analysis and Calorimetry》2013,111(1):971-976

A complex of Lutetium perchloric acid coordinated with l-glutaminic acid (C₅H₉NO₄) and imidazole (C₃H₄N₂), Lu(C₅H₉NO₄)(C₃H₄N₂)₆(ClO₄)₃·5HClO₄·10H₂O was synthesized and characterized. Thermodynamic properties of the complex were studied with an adiabatic calorimeter (AC) from 80 to 390 K and differential scanning calorimetry (DSC) from 100 to 300 K. Two thermal abnormalities were discovered at 220.34 and 248.47 K, which were deduced to be phase transitions. One was interpreted as a freezing-in phenomenon of the reorientational motion of ClO₄ ^? ions and the other was attributed to the orientational order/disorder process of ClO₄ ^? ions. The low-temperature molar heat capacities were measured by AC and the thermodynamic functions [H _T  ? H _298.15] and [S _T  ? S _298.15] were derived in the temperature range from 80 to 390 K with temperature interval of 5 K. Thermal decomposition behavior of the complex was studied by thermogravimetric analysis and DSC.     

New 1D and 2D metal oxygen connectivities in Cu(II) succinato and glutarato coordination polymers: [Cu3(H2O)2(OH)2(C4H4O4)2] · 4H2O, [Cu4(H2O)2(OH)4(C4H4O4)2] · 5H2O and [Cu5(OH)6(C5H6O4)2] · 4H2O

Two Cu(II) hydroxo succinates [Cu₃(H₂O)₂(OH)₂(C₄H₄O₄)₂]?·?4H₂O (1) and [Cu₄(H₂O)₂(OH)₄(C₄H₄O₄)₂]?·?5H₂O (2) and one Cu(II) hydroxo glutarate [Cu₅(OH)₆(C₅H₆O₄)₂]?·?4H₂O (3) have been prepared and structurally characterized by single crystal X-ray diffraction methods. They feature 1D and 2D copper oxygen connectivity of elongated {CuO₆} octahedra in “4?+?1?+?1” and “4?+?2” coordination geometries. Within 1, linear trimers of three edge-sharing {CuO₆} octahedra are connected into copper oxygen chains, which are bridged by the anti conformational succinate anions to generate 2D layers with mono terminally coordinating gauche succinate anions on both sides. The layers are assembled into a 3D framework by interlayer hydrogen bonds with lattice H₂O molecules distributed in channels. Different from 1, the principal building units in 2 are linear tetramers of four edge-sharing {CuO₆} octahedra. The tetramers are condensed into copper oxygen chains and the succinate anions interlink them into a 3D framework with triangular channels filled by lattice H₂O molecules. The {CuO₆} octahedra in 3 are edge-shared to form unprecedented 2D inorganic layers with mono terminally coordinating glutarate anions on both sides. Interlayer hydrogen bonding interactions are responsible for supramolecular assembly of the layers into a 3D framework with lattice H₂O molecules in the channels. The inorganic layers in 3 can be described as hexagonal close packing of oxygen atoms with the Cu atoms in the octahedral cavities. The title compounds were further characterized by elemental analyses, IR spectra and thermal analyses.     

Reactions of SiH2(X̄1A1) with H2, CH4, C2H4, SiH4 and Si2H6 at 298 K

Reaction rate constants of SiH₂(X̄¹A₁) have been directly measured for the first time using the laser photolysis—laser-induced fluorescence method. The preparation of SiH₂ radical in the laser photolysis (193 nm) of phenylsilane and the concentration of the radical is demonstrated by a dye laser at 580.1 nm (X̄¹A₁-Ā¹B₁). The reaction rate constants of SiH₂(X̄¹A₁) with H₂, CH₄, C₂H₄, SiH₄ and Si₂H₆, are 0.001, 0.01, 0.97, 1.1 and 5.7×10⁻¹⁰ cm³ molecule⁻¹ s⁻¹, respectively. For SiH₂(Ā¹B₁(0.2,0)), the collision-free lifetime is 0.6 μs and the quenching rate constant for He is 3.8×10⁻¹⁰ cm³ molecule⁻¹ s⁻¹.     

Syntheses and crystal structures of two Cd(II) coordination polymers: one-dimensional chain [Cd(C4H6N2)2(C4H2O4)(H2O)2] n and two-dimensional sheet [Cd(C4H6N2)(H2O)(C4H4O4)] n · n H2O

Two new Cd(II) coordination polymers, [Cd(C₄H₆N₂)₂(C₄H₂O₄)(H₂O)₂] _n (1) (where C₄H₆N₂?=?2-methylimidazole, C₄H₂O₄?=?fumarate), and [Cd(C₄H₆N₂)(H₂O)(C₄H₄O₄)] _n ?·?nH₂O (2), (where C₄H₄O₄?=?succinates), have been prepared and structurally characterized by single crystal X-ray diffraction. Complex 1 crystallizes in the triclinic space group P 1 in a one-dimensional chain structure, in which carboxy is monodentate; a three-dimensional supermolecular network structure was formed through hydrogen bonding. In complex 2, the coordination geometry of the Cd atoms is a pentagonal bipyramid, and a two-dimensional sheet is formed though carboxyl group bridging. In 1 and 2, IR spectra indicate the presence of bridging carboxyl groups, confirmed by structure analyses.     

Synthesis, IR spectra, and solid-state luminescence of triphenylguanidinium salts with the anions B10H 10 2− , B12H 12 2− , B9C2H 12 2− , [Co(C2B9H11)2]−, and [Ni(C2B9H11)2]−

Triphenylguanidinium Ph₃GH⁺ salts with the anions B₁₀H ₁₀ ^2? , B₁₂H ₁₂ ^2? , B₉C₂H ₁₂ ^2? , [Co(C₂B₉H₁₁)₂]^?, and [Ni(C₂B₉H₁₁)₂]^? were synthesized and described by DTA, IR spectroscopy, and solid-state luminescence. By IR spectroscopy, it was shown that intermolecular interactions involving the NH groups of the cation are enhanced in the sequence [Co(C₂B₉H₁₁)₂]^? ～ [Ni(C₂B₉H₁₁)₂]^? < B₉C₂H ₁₂ ^2? < B₁₂H ₁₂ ^2? < B₁₀H ₁₀ ^2? .     

Syntheses and Structures of Two New Coordination Polymers:[Cu(C14H9O4)(C14H10O4)(C12H12N2)2] and [Ag(C14H9O4)(C13H14N2)]·0.5 H2O

Under hydrothermal conditions, two new ribbon-like structures, [Cu(C14H9O4)-analysis revealed that these structures were constructed by mixed ligands. The coordination polymer forms the basic architecture while the weak interactions extend the framework into a secondary structure. The whole structures of them are governed by collaboration of the strong and weak interactions. Compound 1 crystallizes in monoclinic, space group C2/c with a = 17.0485(3), b =1 1.0558(3), c = 22.7623(4) A, β = 102.465(1)°, V = 4189.2(2) A3, Z = 4, Mr = 915.44, Dc = 1.451g/mL, F(000) = 1900 andμ(MoKα) = 0.587 cm-1. The final R and wR are 0.0030 and 0.1022,respectively for 3037 observed reflections with I ＞ 2σ(I). Compound 2 crystallizes in monoclinic,space group P21/c with a = 11.5963(4), b = 11.7004(5), c = 17.1254(5) A,β = 95.620(1)°, V =2312.4(1) A3, Z = 4, Mr = 556.35, Dc = 1.598 g/mL, F(000) = 1132 andμ(MoKα) = 0.912 cm-1The final R and wR are 0.0431 and 0.1050, respectively for 2629 observed reflections with I ＞ 2σ(I).     

Synthesis, crystal structure, and thermal stability of [Mo2O4(μ2-O)(C6H4O2)2(H2O)] · (C8H9N2)2 · 2H2O

From hydrothermal treatment of benzene-1,2-diamine, pyrocatechol, and MoO₃ in acetic acid solution, a new compound, [Mo₂(μ₂-O)₂(C₆H₄O₂)₂(H₂O)] · (C₈H₉N₂)₂ · 2H₂O (I), constructed from pyrocatechol chelated dinuclear molybdenum units and 2-methylbenzimidazole has been synthesized. Single-crystal structure analysis reveals that the compound crystallizes in the monoclinic space group P2₁/c with a = 23.365(2), b = 7.2214(5), c = 19.3021(16) β = 97.929(4), V = 3225.6(5), Z = 4, M = 808.46, ρ_c = 1.665 g/cm³, μ(MoK _α) = 0.84 mm^?1, F(000) = 1608, the final R = 0.0622 and wR = 0.1484 for 7385 independent reflections with R _int = 0.0393. Interestingly, an in situ condensation between acetic acid and benzene-1,2-diamine has occurred, and the unexpected 2-methyl-1-H-benzo[d] imidazoles serve as counterions and N-H donors to form stable hydrogen-bond network in the crystal. Furthermore, intermolecular hydrogen bonds are found among the cations, anions and crystalline water molecules. The double nuclear molybdenum units are connected by O-H...O hydrogen bonds with the crystalline water molecules to form one-dimensional chains, and the chains are further joined together by N-H...O to form a quasi-two dimensional structure.     

CRYSTAL AND MOLECULAR STRUCTURE OF ο-(2-CYANOETHYL)-p- BROMOBENZOYL-FERROCENE OXIME, CsHsFeC5H4C(C5H4Br)NOC2H4CN

<正> INTRODUCTION. Since some derivatives of alkylating ferrocene were found to be effective catalysts for promoting combustion speed of high energy fuels, research works on ferrocene derivatives have been rapidly developed.     

Synthesis and structure of the organoantimony peroxide solvates [Sb4(μ2-O)4(O2)2(C6H3MeO-2,Br-5)8]·1.5C4H8O2 and [Sb4(μ2-O)4(O2)2(C6H3MeO-2,Br-5)8]·6C4H8O2

The organoantimony peroxide (Ar₂SbO)₄(O₂)₂ (Ar = C₆H₃OMe-2, Br-5) was synthesized by the oxidation of Ar3Sb with hydrogen peroxide in the presence or acetoxime or acetophenone oxime in dioxane. The product crystallizes with various content of the solvent molecules in the crystal unit cell [1.5 (I) and 6 (II), respectively]. An X-ray diffraction analysis of the solvates was performed. Four antimony atoms in the peroxide are in the octahedral coordination, and are linked through bridging oxygen atoms and two peroxide groups. The distances Sb-C, Sb-O_bridge, Sb-O_peroxide, O-O and Sb...Sb are 2.117–2.122, 1.960–1.972, 2.193–2.235, 1.461, 1.465 and 3.223–3.237 Å in I, and 2.112, 2.119, 1.957, 1,966, 2.204, 2,246, 1,467, and 3.2439 Å in II.     

Tetranuclear bismuth complexes Bi4(O)2(O2CC6H2F3-3,4,5)8 · 2C6H6 and Bi4(O)2(O2CC6H2F3-3,4,5)8 · 2C6H4Me2-1,4: Synthesis and structures

X-ray diffraction study of tetranuclear organobismuth complexes Bi₄(O)₂(O₂CC₆H₂F₃-3,4,5)₈ · 2⁶-C₆H₆ and Bi₄(O)₂(O₂CC₆H₂F₃-3,4,5)₈ · 2(C₆H₄Me₂-1,4) revealed four Bi atoms connected through the bridging carboxylate ligands and the O atoms. The coordination sphere of the terminal Bi atoms includes the chelate carboxylate ligand and the 6-arene molecule. The bridging O atoms are tricoordinated, the distances between the terminal Bi atom and the center of benzene molecule (1,4-dimethylbenzene) are 3.024 Å(3.131 Å).Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 1, 2005, pp. 4–11.Original Russian Text Copyright © 2005 by Sharutin, Egorova, Sharutina, Ivanenko, Adonin, Starichenko, Pushilin, Gerasimenko.     

Synthesis and Crystal Structure of [Ni(H2O)6][Ni(H2O)2(C4H2O4)]·4H2O

Reaction of a freshly prepared Ni(OH)_{2?2 x} (CO₃) _x ·yH₂O with maleic acid in H₂O at room temperature afforded [Ni(H₂O)₆][Ni(H₂O)₂(C₄H₂O₄)]·4H₂O, which consists of [Ni(H₂O)₆]²⁺ cations, [Ni(H₂O)₂(C₄H₂O₄)]^2? anions and lattice H₂O molecules. Ni atoms in cations are octahedrally coordinated and Ni atoms in anions are each octahedrally coordinated by bidentate chelating maleato ligands and two water molecules at trans positions. Cations and anions are interlinked by hydrogen bonds to form 1D chains, which are hexagonally arranged and connected by the lattice water molecules. When heated in a flowing argon stream, the compound decomposes, with complete dehydration being followed by dissociation of nickel maleate into NiO and maleic anhydride.     

An infrared and Raman spectroscopic study of Td-type 4,4′-bipyridylcadmium(II) tetracyanometallate (II) benzene (1/2) clathrates: Cd(C10H8N2)Cd(CN)4 · 2C6H6 and Cd(C10H8N2)Hg(CN)4 · 2C6H6

Two new benzene clathrates of the form Cd(4,4-bipyridyl)M(CN)₄ · 2C₆H₆, (M=Cd or Hg) have been prepared in powder form. Their spectral data were compared with those of the corresponding host complexes and found to be consistent with the host structure found in Td-type clathrates.     

Synthesis and Crystal Structure of (C6N3H18)2Ti4O4(C2O4)7·4H2O

The title compound (C6N3H18)2Ti4O4(C2O4)7(4H2O 1 (C13H22N3O18Ti2, Mr = 604.14) was synthesized by the reaction of Ti(SO4)2, H2C2O4(2H2O and N-(2-ammonioethyl)- piperazinium (AEPP) in aqueous solution. The single-crystal X-ray analysis has revealed that 1 crystallizes in the triclinic system, space group Pī with a = 9.1437(6), b = 11.4991(10), c = 11.6975(8)A, α = 96.2915(18), β = 107.998(3), γ = 104.276(4)°, V = 1110.35(14)A3, Z = 2, Dc = 1.807 g/cm3, F(000) = 618, μ = 0.815 mm－1, the final R = 0.0463 and wR = 0.1264 for 3718 observed reflections with I > 2σ(I). X-ray crystal-structure analysis suggests that compound 1 consists of [Ti4O4(C2O4)7]6－ anion and two protonated N-(2-ammonioethyl)piperazinium cations. The anions are linked into an infinite chain through Ti4O4(C2O4)8 by sharing the oxalates as bridging ligands.     

Syntheses,crystal structures and antibacterial activities of [Cu2(C11H11NO5S)2(H2O)4] · 5H2O and [Ni2(C11H11NO5S)2(H2O)4] · 2H2O

The binuclear complexes [Cu₂L₂(H₂O)₄] · 5H₂O (1) and [Ni₂L₂(H₂O)₄] · 2H₂O (2) (where L = C₁₁H₁₁NO₅S, H ₂ L = 2-[(3-formyl-5-methyl-2-hydroxy-benzylidene)-amino]ethanesulfonic acid) have been synthesized and characterized by IR, elemental analysis and X-ray diffraction. The crystals belong to the monoclinic system, space group P2₁/c. Complex 1: a = 16.8902(12), b = 11.2829(6), c = 17.4249(11) Å; β = 106.709(4)°; S = 1.131; V = 3180.5(3) ų; Z = 4; D _Calcd = 1.729 g cm^?3; F(000) = 1712; μ = 1.554 mm^?1; R ₁ = 0.0519, wR ₂ = 0.1349; complex 2: a = 11.399(2), b = 19.985(3), c = 7.3694(10) Å; β = 108.664(7)°; S = 1.157; V = 1590.6(4) ų; Z = 2; D _Calcd = 1.604 g cm^?3; F(000) = 800; μ = 1.388 mm^?1; R ₁ = 0.1859, wR ₂ = 0.4346. The geometry around each metal(II) center can be described as slightly distorted octahedral. Water-sulfonic clusters and (H₂O)₄ water clusters can be observed for 1 from the crystal packing diagram, while cavity and offset face-to-face π–π stacking can be observed for 2. The complexes have been tested for the antibacterial activities which show antibacterial activities of 1 for β-hemolytic streptococcus, Staphylococcus aureus and Escherichia coli, and the antibacterial activity of 2 only for β-hemolytic streptococcus.     

Molar heat capacity and thermodynamic properties of Lu(C5H9NO4)(C3H4N2)6(ClO4)3·5HClO4·10H2O

A complex of Lutetium perchloric acid coordinated with l-glutaminic acid (C₅H₉NO₄) and imidazole (C₃H₄N₂), Lu(C₅H₉NO₄)(C₃H₄N₂)₆(ClO₄)₃·5HClO₄·10H₂O was synthesized and characterized. Thermodynamic properties of the complex were studied with an adiabatic calorimeter (AC) from 80 to 390 K and differential scanning calorimetry (DSC) from 100 to 300 K. Two thermal abnormalities were discovered at 220.34 and 248.47 K, which were deduced to be phase transitions. One was interpreted as a freezing-in phenomenon of the reorientational motion of ClO₄ ^? ions and the other was attributed to the orientational order/disorder process of ClO₄ ^? ions. The low-temperature molar heat capacities were measured by AC and the thermodynamic functions [H _T  ? H _298.15] and [S _T  ? S _298.15] were derived in the temperature range from 80 to 390 K with temperature interval of 5 K. Thermal decomposition behavior of the complex was studied by thermogravimetric analysis and DSC.