Synthesis,Structure and Characterization of Three Metal Molybdate Hydrates: Fe(H2O)2(MoO4)2·H3O,NaCo2(MoO4)2(H3O2)and Mn2(MoO4)3·2H3O

Three metal molybdate hydrates,Fe(H2O)2(MoO4)2·H3O(FeMo),NaCo2(MoO4)2(H3O2)(CoMo)and Mn2(MoO4)3·2H3O(MnMo),were synthesized by the mixed-solvent-thermal methods and characterized by singlecrystal X-ray...     

Synthesis and structure of a three-dimensional lanthanide complex [Tm2(C5H3N(COO)2)3(H2O)3)]·H2O

A new three-dimensional complex [Tm₂(C₅H₃N(COO)₂)₃(H₂O)₃)]·H₂O (PDC?=?3,5-pyridinedicarboxylate), has been synthesized and its structure determined by x-ray single crystal diffraction methods. Complex 1 crystallizes in the monoclinic space group P2(1)/n with a?=?14.579(4), b?=?11.193(3), c?=?14.839(5)?Å, β?=?94.009(6)°, U?=?2415.5(13)?ų. Two independent PDC ligands bridge Tm^III ions from different orientations to form a network. Thermogravimetric analyses on compound 1 show its high structural stability to 410°C.     

Mixed-Metal Oxide Phases Containing Decavanadate Clusters: Synthesis and Crystal Structures of {{(H2O)2K-μ-(H2O)3-M(H2O)3}2[V10O28] (M=Co, Ni)

The synthesis and structures and thermal properties of two compounds: {(H₂O)₂K--(H₂O)₃-Co(H₂O)₃}₂[V₁₀O₂₈] (1) and {(H₂O)₂K--(H₂O)₃-Ni(H₂O)₃}₂[V₁₀O₂₈] (2) are described. These compounds have been prepared by the reaction of aqueous solutions (pH=3.5) of KVO₃with MCl₂·6H₂O (M=Co, Ni) at 70–72°C. The isomorphous structures of the two compounds consist of interlinked chains composed of arrays of {V₁₀O₂₈} clusters which are joined through {(H₂O)₂K--(H₂O)₃-M(H₂O)₃} bridges. Thermogravimetric studies revealed the complete removal of all water molecules in multiple steps in the temperature range 90–208°C.     

2(3 H)呋喃酮向2(5 H)呋喃酮的转化研究

本文研究2(3H)呋喃酮的热转化和碱催化成2(5H)呋喃酮的过程。应用NMR跟踪技术测定了转化动力常数, 计算了活化能, 这对确定适宜的转化条件具有实际指导意义。还对碱催化下的转化机理进行了探讨。     

Reaction of the Binuclear Ruthenium-Platinum Allenyl Complexes (PPh3)2Pt(μ-η1:η2α, β-C(R)=C=CH2)Ru(CO)Cp (R=H, Ph) with (PPh3)AuO3SCF3. The Synthesis and Characterization of a Trimetallic 1:1 Adduct of the Reactants

The reaction of the heterobinuclear metal -allenyl complexes (PPh₃)₂Pt(- ¹: ² _, -C(R)=C=CH₂)Ru(CO)Cp (R=H (1), Ph (2)) with (PPh₃)AuO₃SCF₃ in THF at –78°C to room temperature affords the trimetallic products [(PPh₃)₂Pt( ₂-CO)RuCpAu(PPh₃)( ₃- ¹: ³: ¹-CH₂CCR)]⁺O₃SCF^– ₃ (R=H (3), Ph (4)) in 46 and 55% isolated yield, respectively. The products were characterized by a combination of elemental analysis, FAB mass spectrometry, and IR and ¹H, ¹³C, and ³¹P NMR spectroscopy. The structure of 4 was elucidated by a single-crystal X-ray analysis. The crystal contains discrete trimetallic RuPtAu cations and CF₃SO^– ₃ anions. In the cation, a Pt–Ru bond of 2.7171(6) Å is supported by a semibridging CO and a CH₂CCPh allyl, which is ³-bonded to Ru, and ¹-bonded to each of Pt (through the CPh carbon) and Au (through the central carbon). The Ph₃P–Au–C fragment is close to linear (175.0(2)°), and the coordination environment around Pt is distorted square planar. Complex 3 appears to have the same type of structure as 4 from spectroscopic data.     

Superacid Univalent Metal Phosphites (MH2PO3)2· H3PO3 (M = Rb,Tl(I)) and MH2PO3· H3PO3(M = K,Cs): Synthesis and Structure

By reacting the K, Rb, Cs, or Tl carbonates with excess phosphoric acid, crystals of superacid phosphites, namely, (RbH₂PO₃)₂· H₃PO₃(I), (TlH₂PO₃)₂· H₃PO₃(II), KH₂PO₃· H₃PO₃(III), -CsH₂PO₃· H₃PO₃(IV), and -CsH₂PO₃· H₃PO₃(V), were synthesized. Their structures were determined by single-crystal X-ray diffraction analysis at 150 K. Crystals I: triclinic system, space group , a= 7.713(2) Å, b= 8.679(3) Å, c= 9.235(3) Å, = 79.36(3)°, = 67.60(2)°, = 88.13(3)°, R ₁= 0.0252; crystals II: triclinic system, space group , a= 7.690(3) Å, b= 8.494(3) Å, c= 9.292(4) Å, = 79.48(3)°, = 66.72(3)°, = 85.45(3)°, R ₁= 0.0485; crystals III: monoclinic system, space group P2₁/c, a= 8.726(3) Å, b= 12.182(4) Å, c= 6.354(2) Å, = 104.14(3)°, R ₁= 0.0241; crystals IV: orthorhombic system, space group P2₁2₁2₁, a= 6.033(1) Å, b= 6.444(1) Å, c= 18.345(4) Å, R ₁= 0.0172; crystals Vare monoclinic, space group C2/c, a= 9.990(3) Å, b= 12.197(4) Å, c= 6.866(2) Å. = 118.14(3)°, R ₁= 0.0181. The hydrogen bonding systems form corrugated bands (Iand II), bent layers (III), individual tubes with rectangular cross sections (V), or a three-dimensional framework (IV). A comparative analysis of the crystal structures of acid phosphites with different compositions was performed.     

Structure of (C3H5NH3)2H2P2O7·H2O

The bis(cyclopropylammonium)dihydrogenodiphosphate monohydrate is a new diphosphate associated with the organic molecule C₃H₅NH₂. We report the chemical preparation and the crystal structure of this organic cation diphosphate. (C₃H₅NH₃)₂H₂P₂O₇.H₂O is orthorhombic (S.G. : P2₁2₁2₁), with Z = 4 and the following unit-cell parameters : a = 4.828(1) Å, b = 11.011(1) Å, c = 25.645(2) Å. The P₂O₇ groups and H₂O water molecules form a succession of bidimensional layers perpendicular to the c axis. The organic cations ensure the three-dimensional cohesion by NH-O hydrogen bonds.     

Synthesis and Crystal Structure of a New Copper–PMIDA Compound (H4PMIDA=H2O3PCH2N(CH2CO2H)2)

A new Cu(II)PMIDA compound [Cu(H₂PMIDA)(phen)] 3H₂O (1) (H₄PMIDA = H₂O₃PCH₂N (CH₂CO₂H)₂,phen = 1,10-phenanthroline) has been successfully synthesized and structurally characterized. In complex 1, Cu (II) is six coordinated by chelation in a tetradentate fashion by a PMIDA ligand and by two N atoms of a phen ligand. Every phen–Cu(II)–PMIDA group connects with each other via a hydrogen bond and the edge-to-face -stacking interaction. Complex 1 crystallized in triclinic P-1 with cell dimensions of a = 7.5817(6) Å, b = 10.6980(8) Å, c = 13.1852(10) Å, =82.350(2)°, = 84.151(2)°, =78.4250(2), V= 1035.25(14) ų, Z = 2, Dc = 1.677 Mg/m³.     

Coordination behavior of 1,4-diallylpiperazinium and 1-allyloxybenzotriazole toward silver(I) in the crystalline π-complexes [Ag2(C4H8N2(C3H5)2(H+)2)(H2O)2(NO3)2](NO3)2 and [Ag(C6H4N3(OC3H5)(NO3))]

Reactions of a solution of AgNO₃ in aqueous methanol with solutions of 1,4-diallylpiperazine (acidified with HNO₃ to pH = 4) and 1-allyloxybenzotriazole in ethanol gave the crystalline silver(I) π-complexes [Ag₂(C₄H₈N₂(C₃H₅)₂(H⁺)₂)(H₂O)₂(NO₃)₂](NO₃)₂ (I) and [Ag(C₆H₄N₃(OC₃H₅)(NO₃))] (II). Their crystal structures were determined by X-ray diffraction. Crystals of complexes I and II are monoclinic, space group P2₁/c; for I: a = 7.053(3)Å, b = 9.389(3)Å, c = 15.488(4)Å, β = 91.60°, V = 1025.3(6)ų, Z = 4; for II: a = 10.650(4)Å, b = 15.062(5)Å, c = 7.412(4)Å, β = 104.20(3)°, V = 1152.6(8)ų, Z = 4. In both structures, the organic components act as bidentate ligands forming with AgNO₃ 34- and 14-membered topological rings, respectively. In complex I, the nearly tetrahedral environment of the Ag(I) atom is made up of the olefinic C=C bond, the O atoms of the nitrate anions, and the water molecule. 1-Allyloxybenzotriazole in structure II causes the deformation of the coordination polyhedron of Ag into a trigonal pyramid via inclusion of the ligand N atom in its coordination sphere. The topological units of the complexes form infinite polymer layers linked by anionic NO ₃ ^? bridges. In structure I, these layers are united through a system of hydrogen bonds into a three-dimensional framework.     

[Co(Phen)2(H2O)2](HL)NO3·3H2O的合成及晶体结构

在水溶液中,以邻菲咯啉、丁二酸与硝酸钴为原料合成了一个新的超分子化合物[Co(Phen)2(H2O)2].(HL).(NO3).3H2O,并经元素分析、IR、X射线单晶衍射分析进行了结构表征.结构分析表明,晶体属三斜晶系,P1-空间群,a=0.968 0(2)nm,b=1.370(3)nm,c=1.394 9(3)nm,α=61.714(3)°,β=71.495(4)°,γ=79.575(4)°,V=1.543 7 nm3,Z=2,ρ=1.481 g/cm3,C28H31CoN5O12,Mr=688.51,F(000)=714 andμ=0.627 mm-1,7 754个独立衍射点中,5 428个可观察点满足I≥2σ(I),R1=0.074 5,wR2=0.210 7.晶体中[Co(Phen)2(H2O)2]2+通过π-π相互作用堆积成二维层状结构,层间通过氢键作用构成三维超分子.     

Ir(PCy3)2(H)2(H2B-NMe2)]+ as a latent source of aminoborane: probing the role of metal in the dehydrocoupling of H3B⋅NMe2H and retrodimerisation of [H2BNMe2]2

The Ir^III fragment {Ir(PCy₃)₂(H)₂}⁺ has been used to probe the role of the metal centre in the catalytic dehydrocoupling of H₃B?NMe₂H ( A ) to ultimately give dimeric aminoborane [H₂BNMe₂]₂ ( D ). Addition of A to [Ir(PCy₃)₂(H)₂(H₂)₂][BAr^F₄] ( 1 ; Ar^F=(C₆H₃(CF₃)₂), gives the amine‐borane complex [Ir(PCy₃)₂(H)₂(H₃B?NMe₂H)][BAr^F₄] ( 2 a ), which slowly dehydrogenates to afford the aminoborane complex [Ir(PCy₃)₂(H)₂(H₂B? NMe₂)][BAr^F₄] ( 3 ). DFT calculations have been used to probe the mechanism of dehydrogenation and show a pathway featuring sequential BH activation/H₂ loss/NH activation. Addition of D to 1 results in retrodimerisation of D to afford 3 . DFT calculations indicate that this involves metal trapping of the monomer–dimer equilibrium, 2 H₂BNMe₂ ? [H₂BNMe₂]₂. Ruthenium and rhodium analogues also promote this reaction. Addition of MeCN to 3 affords [Ir(PCy₃)₂(H)₂(NCMe)₂][BAr^F₄] ( 6 ) liberating H₂B? NMe₂ ( B ), which then dimerises to give D . This is shown to be a second‐order process. It also allows on‐ and off‐metal coupling processes to be probed. Addition of MeCN to 3 followed by A gives D with no amine‐borane intermediates observed. Addition of A to 3 results in the formation of significant amounts of oligomeric H₃B?NMe₂BH₂?NMe₂H ( C ), which ultimately was converted to D . These results indicate that the metal is involved in both the dehydrogenation of A , to give B , and the oligomerisation reaction to afford C . A mechanism is suggested for this latter process. The reactivity of oligomer C with the Ir complexes is also reported. Addition of excess C to 1 promotes its transformation into D , with 3 observed as the final organometallic product, suggesting a B? N bond cleavage mechanism. Complex 6 does not react with C , but in combination with B oligomer C is consumed to eventually give D , suggesting an additional role for free aminoborane in the formation of D from C .     

Schiff碱配合物Cd(H2SalN)2(OAc)2(H2O)]·3(H2O)的合成与结构

用一步法合成了一个Schiff碱配合物[Cd(H2SalN)2(OAc)2(H2O)]·3(H2O)(H2SalN=salicylaldehyde isonicotinoylhydrazone),并用IR和X射线单晶衍射进行了结构测定.该化合物属于三斜晶系,P-1空间群,晶胞参数为:a =1.554 4(3) nm,b...     

~1H(P)、~2H(D)、~3H(T)核磁共振

一般来说,元素氢有三种同位素,即氢~1H或氕P,重氢~2H或氘D以及超重氢~3H或氚T。它们的原子核组成不同,因此核性质亦有所差别(见表1)。     

[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     

K3[Fe3.26V0.74(OH)O(PO4)4(H2O)2]·2H2O: a synthetic leucophosphite

A new iron(III)/vanadium(III) phosphate, K₃[Fe_3.26V_0.74(OH)O(PO₄)₄(H₂O)₂]·2H₂O (1), has been obtained by hydrothermal synthesis and characterized by single crystal X-ray diffraction, Scanning electron microscopy–energy dispersive X-ray spectroscopy, Inductively coupled plasma atomic emission spectroscopy (ICP), thermogravimetric analysis, and FTIR spectroscopy. Single crystal X-ray diffraction reveals a 3D open framework (monoclinic, space group P2₁/n, a?=?9.6391(7)?Å, b?=?9.8063(7)?Å, c?=?9.7268(7)?Å, β?=?100.71(1)°, and V?=?903.38(11)?ų). This structure presents Fe^III and V^III in a 4.4?:?1?M ratio with the metal ions in two different crystallographic sites. Both metallic centers have distorted octahedral environments, linked by PO₄ tetrahedra, forming channels along the a-axis. The asymmetric unit of K₃[Fe_3.26V_0.74(OH)O(PO₄)₄(H₂O)₂]·2H₂O presents a {M₄(OH)O(PO₄)₄(H₂O)₂}^3? anionic entity, charge balanced by three K⁺, which are located within the channels. It is also possible to distinguish M₄O₂ units whose M^III polyhedra are linked by vertex and edges.     

Comparison of the Bonding of Benzene and C60 to a Metal Cluster: Ru3(CO)9(μ3-η2,η 2,η2-C6H6) and Ru3(CO)9(μ3-η2,η2,η2-C60)

The electron distributions and bonding in Ru₃(CO)₉( ³- ², ², ²-C₆H₆) and Ru₃(CO)₉( ³- ², ², ²-C₆₀) are examined via electronic structure calculations in order to compare the nature of ligation of benzene and buckminsterfullerene to the common Ru₃(CO)₉ inorganic cluster. A fragment orbital approach, which is aided by the relatively high symmetry that these molecules possess, reveals important features of the electronic structures of these two systems. Reported crystal structures show that both benzene and C₆₀ are geometrically distorted when bound to the metal cluster fragment, and our ab initio calculations indicate that the energies of these distortions are similar. The experimental Ru–C_fullerene bond lengths are shorter than the corresponding Ru–C_benzene distances and the Ru–Ru bond lengths are longer in the fullerene-bound cluster than for the benzene-ligated cluster. Also, the carbonyl stretching frequencies are slightly higher for Ru₃(CO)₉( ³- ², ², ²-C₆₀) than for Ru₃(CO)₉( ³- ², ², ²-C₆H₆). As a whole, these observations suggest that electron density is being pulled away from the metal centers and CO ligands to form stronger Ru–C_fullerene than Ru–C_benzene bonds. Fenske-Hall molecular orbital calculations show that an important interaction is donation of electron density in the metal–metal bonds to empty orbitals of C₆₀ and C₆H₆. Bonds to the metal cluster that result from this interaction are the second highest occupied orbitals of both systems. A larger amount of density is donated to C₆₀ than to C₆H₆, thus accounting for the longer metal–metal bonds in the fullerene-bound cluster. The principal metal–arene bonding modes are the same in both systems, but the more band-like electronic structure of the fullerene (i.e., the greater number density of donor and acceptor orbitals in a given energy region) as compared to C₆H₆ permits a greater degree of electron flow and stronger bonding between the Ru₃(CO)₉ and C₆₀ fragments. Of significance to the reduction chemistry of M₃(CO)₉( ³- ², ², ²-C₆₀) molecules, the HOMO is largely localized on the metal–carbonyl fragment and the LUMO is largely localized on the C₆₀ portion of the molecule. The localized C₆₀ character of the LUMO is consistent with the similarity of the first two reductions of this class of molecules to the first two reductions of free C₆₀. The set of orbitals above the LUMO shows partial delocalization (in an antibonding sense) to the metal fragment, thus accounting for the relative ease of the third reduction of this class of molecules compared to the third reduction of free C₆₀.     

Syntheses and structures of p-HOOCC6F4COOH · H2O (H2L · H2O) and luminescent coordination polymers [Tb2(H2O)4(L)3 · 2H2O] n and Tb2(Phen)2(L)3 · 2H2O

Compounds p-HOOCC₆F₄COOH · H₂O (H₂L · H₂O), [Tb₂(H₂O)₄(L)₃ · 2H₂O] _n (I), and Tb₂(Phen)₂(L)₃ · 2H₂O (II) are synthesized. According to the X-ray structure analysis data, the crystal structure of H₂L · H₂O is built of centrosymmetric molecules H₂L and molecules of water of crystallization. The crystal structure of compound I is built of layers of coordination 2D polymer [Tb₂(H₂O)₄(L)₃] _n and molecules of water of crystallization. The ligands are the L^2? anions performing both the tetradentate bridging and pentadentate bridging-chelating functions. The coordination polyhedron TbO₉ is a distorted three-capped trigonal prism. Acid H₂L manifests photoluminescence in the UV region (??_max = 368 nm). Compounds I and II have the green luminescence characteristic of the Tb³⁺ ions, and the band with ??_max = 545 nm (transition ⁵ D ₄?? ⁷ F ₅) is maximum in intensity. The photoluminescence intensity of compound II is higher than that for compound I.     

A three-dimensional porous metal-organic framework based on 9,9-dimethylfluorene-2,7-dicarboxylic acid (H2MFDA): {[Tb2(MFDA)3(DMF)2(H2O)3] · (H2O)3(DMF)6} n

The title metal-organic framework, [Tb₂(MFDA)₃(DMF)₂(H₂O)₃] · (H₂O)₃(DMF)₆} _n (I) (H₂MFDA = 9,9-dimethylfluorene-2,7-dicarboxylic acid, DMF = N,N-dimethylformamide), has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction (CIF file CCDC no. 995892). Complex I crystallizes in triclinic space group \(P\bar 1\) with a = 13.0022(3), b = 13.3793(3), c = 25.8929(4) Å, α = 84.060(2)°, β = 88.104(2)°, γ = 66.361(2)°, V = 4104.05(15) ų, C₇₅H₁₀₄N₈O₂₆Tb₂, M = 1851.50, ρ _c = 1.498 g/cm³, μ(MoK _α) = 1.790 mm^?1, F(000) = 1896, GOF = 1.055, Z = 2, the final R ₁ = 0.0522 and wR ₂ = 0.1380 for I > 2σ(I). In MOF I, the Tb₂ dinuclear units double-bridged by two carboxylate groups are connected together by MFDA ligands to give rise to a 3D architecture that consists in two types of 1D open channels along the y axis with about 6 × 8 and 9 × 12 Ų dimensions. The solvent accessible space for the desolvated I is 53.4% of the total volume. The 3D structure can also be rationalized as a six-connected (3.4¹¹.5².6) topological network by considering the Tb₂ dinuclear units as six-connected nodes and MFDA ligands as linkers, respectively.     

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.     

Unique seven-node rare-earth octacyanomolybdate(IV) three-dimensional molecular frameworks: {[Er(H2O)5(Er(H2O)4)3][Mo(CN)8]3·11H2O}n and {[Eu(H2O)5(Eu(H2O)4)3][Mo(CN)8]3·11H2O}n

The crystal structure analyses of {[Er(H₂O)₅(Er(H₂O)₄)₃][Mo(CN)₈]₃·11H₂O}_n (1) and {[Eu(H₂O)₅(Eu(H₂O)₄)₃][Mo(CN)₈]₃·11H₂O}_n (2), show that they are not only new neutral three-dimensional rare-earth octacyanomolybdate(IV) molecular frameworks, but that they also belong to an unknown structure type having seven different nodes. To the best of our knowledge this is different to any other known molybdenum(IV) octacyanide complexes published to date. Both compounds crystallize in the triclinic system, space group P-1, and are isostructural and isotypic. The coordination polyhedra of the molybdenum atoms in the three different [Mo(CN)₈]⁴⁻ anions are trigonal prisms, with two additional atoms. A new bridging mode for octacyanometallates is also observed with five of the eight cyanide groups involved in bridging either three or four rare-earth atoms, while the three remaining cyanide groups are terminal and are involved in hydrogen bonding. The four rare-earth atoms in 1 and 2 have different coordination polyhedra in the form of trigonal prisms with two additional atoms. The three-dimensional structures are made up of infinite two-dimensional slabs linked by one of the rare-earth metal atoms. In both compounds, apart from the 17 coordinated water molecules, there are 11 lattice water molecules of crystallization present in the cavities of the three-dimensional frameworks. The 28 water molecules and the terminal CN⁻ groups are involved in an extensive O–H⋯O and O–H⋯N hydrogen bonding network.