Nonisothermal Kinetice of Dehydration Process of [Sm(m-CIBA)3phen]2·2H2O and[Sm(p-CIBA)3phen]2·2H2O

Compounds[Sm(m-CIBA)3phen]2·2H2O and[Sm(p-ClBA)3phen]2·2H2O(m-ClBA=m-chlorobenzoate,PClBA=p-chlorobenzoate,phen=1,10-phenanthroline)were prepared.The dehydration processes and kinetics of these compounds were studied from the analysis of the DSC curves using a method of processing the data of thermal analysis kinetics.The Arrhenius equation for the dehydration process can be expressed as lnk=38.65-243.90x103|RT for and△S≠ of dehydration reaction for the title compounds are determined,respectively.     

Non-isothermal Decomposition Kinetics of Complexes [ Sm(m-MBA)3 phen]2 and [ Sm(o-MOBA)3 phen] 2·2H2O

Introduction In recent years, there has been considerable interest in complexes formed by lanthanide cations and various benzoate derivatives[1-4], due to their potential application in areas, such as extraction, separation,germicide preparation, catalysis, luminescence, and functional material preparation[5].     

Structure of Coordination Polymer,[Zn (bipy) (H2O) 3SO4] · 2H2O (bipy = 4,4'-bipyridine)

The crystal of the title compound (C10H18N2O9SZn Mr= 407. 69) belongs to the hexagonal system, space group P65 with cell parameters: a= 11. 411(2), c=20. 908(4) A, V=2357.7(7)A 3, Z=6, Dc=1. 723g/cm3, F(000)=1260,μ(MoKα) =1. 743mm-1. The final R and wR factors are 0. 072 and 0. 178 respectively for 1335 observed reflections. In the structure, zinc ions are bridged by 4,4'-bipyridine to form infinite chains. The sheets containing parallel chains stack along a 65 screw axis to give a helical staircase motif. The helical structure is mainly controlled by the hydrogen bonds.     

Nonisothermal Kinetics of Dehydration Process of [Sm（m-CIBA）3phen]2·2H2O and [Sm（p-CIBA）3phen]2·2H2O

Compounds [Sm（m-CIBA）3phen]2.2H20 and [Sm（p-CIBA）3phen]2·2H20（m-CIBA=m-chlorobenzoate, pClBA=p-chlorobenzoate, phen=l,10-phenanthroline） were prepared. The dehydration processes and kinetics of these compounds were studied from the analysis of the DSC curves using a method of processing the data of thermal analysis kinetics. The Arrhenius equation for the dehydration process can be expressed as lnk=-38.65-243.90×l0^3/RT for [Sm（m-CIBA）3phen]2·2H2O, and lnk=38.70-172.22×103/RT for [Sm（p-CIBA）3phen]2·2H2O. The values of △H^1, △G^1, and △S^1 of dehydration reaction for the title comnonnds are determined respectively.     

Synthesis and Structure of anti-Configuration Complex [Cu(tssb)2]·2[(H3O)Cl]·4H2O

The title complex [Cu(tssb)2]·2[(H3O)Cl]·4H2O (C18H34Cl2CuN2O14S2) (tssb = taurine salicylaldehyde Schiff base) has been synthesized by the reaction of taurine salicylaldehyde Schiff base (tssb) and copper acetate in water-ethanol. Its single-crystal structure was determined by X-ray diffraction method. The crystal structure belongs to triclinic, space group P with a = 0.7407(1), b = 1.3329(3), c = 1.5736(3)nm, α = 103.800(4), β = 95.030(4), γ = 104.416(4)°, Mr = 701.06, V = 1.4433(5) nm3, Z = 2, Dc = 1.613 g/cm3, μ = 1.153 mm-1 and F(000) = 726. The compound is an infinitely expanding three-dimensional network connected with hydrogen bonds. The Cu(Ⅱ) atom is coordinated by two nitrogen and two oxygen atoms to form a distorted planar coordination compound which adopts anti-configuration because two sulfonic acid groups are positioned diagonally on a plane.     

Syntheses, Crystal Structures and Characterization of Two Zeotype Crystals of K4[Cr3O(H2O)3(OOCH)6]2[P2W18O62] ·9.5H2O and K4[Cr3O(H2O)3(OOCH)6[H3P2W17Co(H2O)O61]·20H2O

Two novel zeotype crystals, K4[Cr3O(H2O)3(OOCH)6]2[P2W18O62]·9.5H2O(1) and K4 [Cr3O(H2O)3·X-ray single crystal diffraction. Crystal data: C12H43O103.5K4Cr6P2W18(1), hexagonal P6(3)/m, a=1.5895(2)nm, b=1.5895(2) nm, c=2.1620(4) nm, α=90°, β=90°, γ =120°, V=4.7305(13) nm3, Z=2,R1 =0. 0726, wR2=0. 1542; C6H57O98K4Cr3CoP2W17(2), hexagonal P6(3)/mmc, a=1. 61328 (3) nm, b=1.61328(3) nm, c=2. 06613 (9) nm, α=90°,β=90°, γ=120°, V=4. 6570(2) nm3, Z=2, R1=0. 0377,wR2 =0.1070. These crystals were characterized using elemental analysis, IR, TG-DTA, and XRD. It was found that the polyoxometalate anions maintained Wells-Dawson structure for crystal 1 and lacunary Wells-Dawson structure for crystal 2. Thermal analysis showed that crystal 1 lost the water of crystallization at 132 ℃, whereas crystal 2 lost the water of crystallization at 100 ℃. Crystal 1 could reversibly desorb and adsorb water molecules and its crystal structure could be restored after re-adsorbing the water molecules. It was also found from the XRD patterns that the void size of crystal 2 is smaller compared with that of crystal 1, which is attributed to the higher anion charges.     

Thermochemical study of [Sm(C7H5O3)2·(C4H6NO2S)]·2H2O

The product from reaction of samarium chloride hexahydrate with salicylic acid and Thioproline, [Sm(C₇H₅O₃)₂·(C₄H₆NO₂S)]·2H₂O, was synthesized and characterized by IR, elemental analysis, molar conductance, and thermogravimetric analysis. The standard molar enthalpies of solution of [SmCl₃·6H₂O(s)], [2C₇H₆O₃(s)], [C₄H₇NO₂S(s)] and [Sm(C₇H₅O₃)₂·(C₄H₇NO₂S)·H₂O(s)] in a mixed solvent of absolute ethyl alcohol, dimethyl sulfoxide(DMSO) and 3 mol L^?1 HCl were determined by calorimetry to be Δ_s H _m ^Φ [SmCl₃ δ6H₂O (s), 298.15 K]= ?46.68±0.15 kJ mol^?1 Δ_s H _m ^Φ [2C₇H₆O₃ (s), 298.15 K]= 25.19±0.02 kJ mol^?1, Δ_s H _m ^Φ [C₄H₇NO₂S (s), 298.15 K]=16.20±0.17 kJ mol^?1 and Δ_s H _m ^Φ [Sm(C₇H₅O₃)₂·(C₄H₆NO₂S)]·2H₂O (s), 298.15 K]= ?81.24±0.67 kJ mol^?1. The enthalpy change of the reaction (1) $$ SmCl_3 \cdot 6H_2 O(s) + 2C_7 H_6 O_3 (s) + C_4 H_7 NO_2 S(s) = Sm(C_7 H_5 O_3 )_2 \cdot (C_4 H_6 NO_2 S) \cdot 2H_2 O(s) + 3HCl(g) + 4H_2 O(1) $$ was determined to be Δ_s H _m ^Φ =123.45±0.71 kJ mol^?1. From date in the literature, through Hess’ law, the standard molar enthalpy of formation of Sm(C₇H₅O₃)₂(C₄H₆NO₂S)δ2H₂O(s) was estimated to be Δ_s H _m ^Φ [Sm(C₇H₅O₃)₂·(C₄H₆NO₂S)]·2H₂O(s), 298.15 K]= ?2912.03±3.10 kJ mol^?1.     

The solid-state thermal decomposition of Sr3[La(C2O4)3(H2O)2]2·11H2O

Strontium(II)diaquatris(oxalato)lanthanate(III)unidecahydrate, Sr₃[La(C₂O₄)₃(H₂O)₂]₂·11H₂O, has been synthesized and characterized by elemental, IR and electronic spectral studies. Thermal studies (TG, DTG and DTA) in air showed that all the crystal and coordinated water molecules are removed at ca. 225 °C. The final end product at 1,000 °C was shown to be a mixture of mainly SrCO₃, Sr₃La₄O₉ and La₂Sr₂O₅ along with oxides and carbides of both the metal, through the formation of an intermediate mixture of likely SrC₂O₄ and La₂(C₂O₄)_2.8 at 282 °C, and SrCO₃ and La₂O(CO₃)₂ at 540 °C. The multi-step dehydration and decomposition of the compound has been explored from the DSC study in nitrogen up to 670 °C, and the evaluated kinetic parameters are discussed.     

[Gd(Gly)3(H2O)2]Cl3·H2O的合成与晶体结构

氯化钆;甘氨酸;固态配合物;[Gd(Gly)3(H2O)2]Cl3·H2O的合成与晶体结构     

On the thermal decomposition of [Fe2NiO(CH3COO)6(H2O)3]·2H2O

The heteronuclear-oxoacetate with the composition [Fe₂NiO(CH₂COO)₆(H₂O)₃]·2H₂O decomposed on heating, forming nickel ferrite NiFe₂O₄ and (depending on the decomposition conditions) in part other solid phases. H₂O, CH₃COOH, acetone and CO₂ were also formed in the decomposition. A reaction scheme is given for the decomposition. The products were porous powders with grain diameters between 3 and 10m. On increase of the temperature of decomposition from 300 to 800 C, the BET surface area and the surface area of the pores decreased, but only a small alteration in grain size was observed. As a result of thermal treatment in the temperature region abone 800C, larger aggregates of grains were formed in sintering processes.

---

Zusammenfassung Heteronukleare-Oxoazetate der Zusammensetzung [Fe₂NiO(CH₃COO)₆(H₂O)₃]·2H₂O werden durch Erhitzen zersetzt, wobei Nickelferrite NiFe₂O₄ und — in AbhÄngigkeit von den Bedingungen der Zersetzung — mit einem Teil anderer fester Phasen gebildet wird. In der Zersetzungsreaktion werden auch H₂O, CH₃COOH, Azeton und CO₂ gebildet. Es wird ein Reaktionsschema für die Zersetzung angegeben. Die Produkte sind poröse Pulver mit einem Korndurchmesser zwischen 3 und 10 m. Wird die Zersetzungstemperatur von 300 auf 800C erhöht, nimmt die BET-OberflÄche und die PorenoberflÄche ab, wobei sich die Korngrö\e aber nur wenig verÄndert. Im Ergebnis der WÄrmebehandlung im Temperaturbereich oberhalb 800C werden durch Sinterprozesse grö\ere Partikelaggregate gebildet.

     

化合物[H3DETA]3[H2DETA]2[Pr(SiW11O39)2]·2H2O的水热合成及晶体结构

通过水热合成制得了硅钨杂多酸镨化合物[H3DETA]3[H2DETA]2[Pr(S iW11O39)2].2H2O[DETA:二乙烯三胺].晶体结构解析表明:该化合物属于三斜晶系,P1-空间群,a=1.200 0(2)nm,b=2.026 1(4)nm,c=2.239 2(5)nm,α=111.60(3)°,β=92.92(3)°,γ=103.56(3)°;V=4.863 8(17)nm3,Z=2,ρ=4.152 g/cm3,μ=26.519 mm-1,F(000)=5 374.化合物中Pr3+键合两个[S iW11O39]8-构成一个[Pr(S iW11O39)2]13-多阴离子,Pr3+与两个[S iW11O39]8-阴离子的八个氧原子配位构成一个畸变的四方反棱柱.此外,多阴离子[Pr(S iW11O39)2]13-和有机分子还通过氢键形成一个大的空腔.     

Synthesis of calcium titanate from [Ca(H2O)3]2[Ti2(O2)2O(NC6H6O6)2]·2H2O as a cheap single-source precursor

Calcium titanate (CaTiO₃) was conveniently synthesized by thermal decomposition of a single-source precursor [Ca(H₂O)₃]₂[Ti₂(O₂)₂O(NC₆H₆O₆)₂]·2H₂O at low temperature. This single-source precursor was characterized by elemental analysis, IR spectrum, thermal gravimetric analysis and X-ray single crystal diffraction. The calcined products at different temperature were further characterized by powder X-ray diffractions and IR spectra. The morphology, microstructure, and crystallinity of the resulting CaTiO₃ materials have been characterized by SEM and TEM. The BET measurement revealed that the CaTiO₃ powders had a surface area of 14.0 m²/g. In addition, the microwave dielectric properties of the resulting CaTiO₃ material have been measured.     

Structure of the complex [trans-SnF4(H2O)2· (18-crown-6)· 2H2O]

The molecular and crystal structure of the title complex (I) obtained by addition of tin fluoride in a hydrofluoric acid solution to 18-crown-6 in methanol was investigated by X-ray structure analysis. The crystals are monoclinic, space group P2₁/n, a = 13.497(3), b = 7.806(2), c = 9.892(2) Å, β = 95.57(3)°, Z = 2 for C₁₂H₃₂F₄O₁₀Sn. In the polymer chain, the crown ether molecules alternate with the inorganic complexes [trans-SnF₄(H₂O)₂] and are linked to them by O-H...O type hydrogen bonds involving the intermediate water molecules. The weak C-H...F interactions bind the chains into the layers which are parallel to the xz plane.     

Formation of [FeW12O40]5− under hydrothermal conditions: syntheses,crystal structures,and characterization of [Fe(2,2′-bipy)3]2[HFeW12O40] · 5H2O and (4,4′-H2bipy)6(Hpy)2(H3O)[FeW12O40]3 · 11H2O

Two supramolecular compounds based on tungstoferrate [FeW₁₂O₄₀]^5?, [Fe^II(2,2′-bipy)₃]₂[HFeW₁₂O₄₀] · 5H₂O (1), and [Hpy]₂[4,4′-H₂bipy]₆(H₃O)[FeW₁₂O₄₀]₃ · 11H₂O (2) (py = pyridine, bipy = bipyridine) were synthesized hydrothermally and characterized structurally. The hydrogen bonds between polyoxoanions and water and the edge-to-face π–π interaction between [Fe^II(2,2′-bipy)₃]²⁺ with a shortest C–C distance of 3.513 Å are the main forces to construct the 3-D architecture of 1. In 2, a 3-D supramolecular architecture is assembled by the tungstoferrate anions, protonated 4,4′-bipy cations, and water through hydrogen bonding. The variable-temperature magnetic susceptibilities indicate that 1 is paramagnetic with μ _eff corresponding to one Fe(III) with spin-only contribution, showing that Fe in the coordination cations has a +II oxidation number and low spin state.     

Synthesis and structure of [Cr3O(CH3COO)6(H2O)3][UO2 (CH3COO)3] · 3H2O

Crystals of [Cr₃O(CH₃COO)₆(H₂O)₃][UO₂(CH₃COO)₃]·3H₂O (I) were synthesized for the first time and studied by X-ray crystallography. The crystals of I are orthorhombic: a = 8.3561(3) ?, b = 16.8421(5) ?, c = 25.7448(9) ?, V = 3623.2(2) ?³, space group P2₁2₁2₁, Z = 4, R = 0.0409. The structure is composed of trinuclear [Cr₃O(CH₃COO)₆(H₂O)₃]⁺ complexes and mononuclear [UO₂(CH₃COO)₃]^? complexes classified with crystal-chemical groups A₃M³B ₆ ² M ₃ ¹ (A = Cr³⁺, M³ = O^2?, B² = CH₃COO^?, M¹ = H₂O) and AB ₃ ⁰¹ (A = UO ₂ ²⁺ , B⁰¹ = CH₃COO^?), respectively. The complexes are bound to each other by electrostatic interactions and hydrogen bonds involving outer-sphere water molecules. The results of IR spectroscopic study of I are in good agreement with the structural data for the crystal.     

[Er(nmp)4(H2O)3]H[SiMo12O40]·2nmp·0.5H2O的合成、性质与晶体结构

由Er2O3、H4SiMo12O40和nmp合成了分子组成为[Er(nmp)4(H2O)3]H[SiMo12O40]2nmp0.5H2O(nmp=N-甲基吡咯烷酮)的配合物,并通过单晶X-射线衍射测定了晶体结构。结果表明,该化合物属单斜晶系,P21/c空间群,晶胞参数a=17.4601(7),b=18.1906(5),c=22.9096(8)?b=105.2980(10),Z=4,V=7018.5(4)3,Dc=2.504g/cm3,R=0.0460,wR=0.1114,F(000)=5064.配合物中Er3+以七配位的单加冠三棱柱构型配阳离子形式存在,与之配位的是4个N-甲基吡咯烷酮和3个H2O分子,该配阳离子与[SiMo12O40]4-阴离子通过静电作用相结合。     

Binary group 15 polyazides. structural characterization of [Bi(N3)4]-, [Bi(N3)5]2-, [bipy·Bi(N3)5]2-, [Bi(N3)6]3-, bipy·As(N3)3, bipy·Sb(N3)3, and [(bipy)2·Bi(N3)3]2 and on the lone pair activation of valence electrons

The binary group 15 polyazides As(N(3))(3), Sb(N(3))(3), and Bi(N(3))(3) were stabilized by either anion or donor-acceptor adduct formation. Crystal structures are reported for [Bi(N(3))(4)](-), [Bi(N(3))(5)](2-), [bipy·Bi(N(3))(5)](2-), [Bi(N(3))(6)](3-), bipy·As(N(3))(3), bipy·Sb(N(3))(3), and [(bipy)(2)·Bi(N(3))(3)](2). The lone valence electron pair on the central atom of these pnictogen(+III) compounds can be either sterically active or inactive. The [Bi(N(3))(5)](2-) anion possesses a sterically active lone pair and a monomeric pseudo-octahedral structure with a coordination number of 6, whereas its 2,2'-bipyridine adduct exhibits a pseudo-monocapped trigonal prismatic structure with CN 7 and a sterically inactive lone pair. Because of the high oxidizing power of Bi(+V), reactions aimed at Bi(N(3))(5) and [Bi(N(3))(6)](-) resulted in the reduction to bismuth(+III) compounds by [N(3)](-). The powder X-ray diffraction pattern of Bi(N(3))(3) was recorded at 298 K and is distinct from that calculated for Sb(N(3))(3) from its single-crystal data at 223 K. The [(bipy)(2)·Bi(N(3))(3)](2) adduct is dimeric and derived from two BiN(8) square antiprisms sharing an edge consisting of two μ(1,1)-bridging N(3) ligands and with bismuth having CN 8 and a sterically inactive lone pair. The novel bipy·As(N(3))(3) and bipy·Sb(N(3))(3) adducts are monomeric and isostructural and contain a sterically active lone pair on their central atom and a CN of 6. A systematic quantum chemical analysis of the structures of these polyazides suggests that the M06-2X density functional is well suited for the prediction of the steric activity of lone pairs in main-group chemistry. Furthermore, it was found that the solid-state structures can strongly differ from those of the free gas-phase species or those in solutions and that lone pairs that are sterically inactive in a chemical surrounding can become activated in the free isolated species.     

COMPLEX SALTS [Pd(NH3)4][Pd(NH3)3NO2] [CrOx3]·H2O AND [Pd(NH3)4][Pd(NH3)3NO2] [CoOx3]·H2O AND SOLID SOLUTIONS [Pd(NH3)4] [Pd(NH3)3NO2][CoOx3]x[RhOx3]1–x·H2O : PROMISING PRECURSORS FOR POROUS NANOALLOYS

Journal of Structural Chemistry - New complex salts [Pd(NH3)4][Pd(NH3)3NO2][CrOx3]·H2O I, [Pd(NH3)4][Pd(NH3)3NO2][CoOx3]·H2O II, and a series of solid solutions...     

CRYSTAL STRUCTURE OF [Sm(CCl_3COO)_3(H_2O)_2]·2H_2O

<正> Biaqua-trichloroacetate-samarium dihydrate, [Sm(CCl3COO)3(H2O)2]-2H2O, Mr=707.54, orthorhombic, space group Pnne, with a = 19.158(5), b = 22.176(4), c= 9.798(4)A, Z= 8, V= 4162.7A3.F{000)= 2696,λ(MoKα)=0.71069A, Dx = 2.258 g/cm3, final R=0.061. The title compound has non-molecular structural character, and its structural units Sm(μ-CCl3COO)s/2-(H2O>2 constitute 2-dinensional infinite chains of Sm(μ-CCl3COO)4Sm(μ-CCl3-COO)2Sm.The Sa(Ⅲ) atom in each unit is bound to two O atoms from aqua-molecules and six 0 atoms from six bridging CCl3COO groups (four of which are shared with the SB atom of another unit, two shared with the Sm atom of a third unit) forming a square antiprism.