Synthesis and characterization of a new layered gallium phosphate [Co(en)3][Ga3(H2PO4)6(HPO4)3] templated by cobalt complex

A new layered gallium phosphate [Co(en)₃][Ga₃(H₂PO₄)₆(HPO₄)₃], denoted as GaPO-CJ14, has been synthesized solvothermally by using a racemic mix of chiral metal complex Co(en)₃Cl₃ as a template. Its structure was determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, ICP, and TG analyses. The compound crystallizes in the monoclinic space group P2₁/m (No. 11) with a=9.2103(3), b=22.0936(8), c=9.5458(4) Å, β=108.278(2)°, Z=2, R₁=0.0497 and wR₂=0.1122 for all data. The inorganic layer is built up by alternation of Ga-centered octahedra (GaO₆) and P-centered tetrahedra (PO₃(OH), PO₂(OH)₂ , PO₂(O)(OH) and PO(O)(OH)₂) forming a 4.12-net. The sheet structure is featured by a series of structural units composed of two centrosymmetrically related [3.3.3] propellane-like chiral motifs. The metal complex cations locate in the interlayer region and interact with the host network through H-bonds.     

[H3N(CH2)4NH3]2[Al4(C2O4)(H2PO4)2(PO4)4]·4[H2O]: A new layered aluminum phosphate-oxalate

A new layered inorganic-organic hybrid aluminum phosphate-oxalate [H₃N(CH₂)₄NH₃]₂[Al₄(C₂O₄)(H₂PO₄)₂(PO₄)₄]·4[H₂O](AlPO-CJ25) has been synthesized hydrothermally, by using 1,4-diaminobutane (DAB) as structure-directing agent. The structure has been solved by single-crystal X-ray diffraction analysis and further characterized by IR, ³¹P MAS NMR, TG-DTA as well as compositional analyses. Crystal data: the triclinic space group P-1, a=8.0484(7) Å, b=8.8608(8) Å, c=13.2224(11) Å, α=80.830(6)°, β=74.965(5)°, γ=78.782(6)°, Z=2, R_1[I>2σ(I)]=0.0511 and wR_{2(all data)}=0.1423. The alternation of AlO₄ tetrahedra and PO₄ tetrahedra gives rise to the four-membered corner-sharing chains, which are interconnected through AlO₆ octahedra to form the layered structure with 4,6-net sheet. Interestingly, oxalate ions are bis-bidentately bonded by participating in the coordination of AlO₆, and bridging the adjacent AlO₆ octahedra. The layers are held with each other through strong H-bondings between the terminal oxygens. The organic ammonium cations and water molecules are located in the large cavities between the interlayer regions.     

Synthesis,spectroscopic and structural investigation of Zn(NCS)2(nicotinamide)2 and [Hg(SCN)2(nicotinamide)]n

Zinc(II) and mercury(II) thiocyanate complexes with nicotinamide, bis(nicotinamide-N)-bis(thiocyanato-N)zinc(II) (1) and catena-[nicotinamide-N-(μ-thiocyanato-S,N)(thiocyanato-S)mercury(II)] (2), have been prepared and characterized by spectroscopic, thermal and X-ray crystallographic methods. The vibrational bands of diagnostic value are compared to the values of the free ligand and the data are in good correlation with the X-ray results. Centrosymmetrical hydrogen bonded dimers are found, R₂²(10) in 1 and R₂²(8) in 2.     

炔烃桥和氢桥铍化合物中铍原子的共价

根据作者之一提出的共价的新定义，用DV－X_αSCC和自然健轨道法研究了[MeBe(C≡CMe)NMe_3]_2，[Be(C≡CR)_2]_n，[MeBeH·NMe_3]及(BeH_2)_n等化合物中铍原子的共价．结果表明，在这几种化合物中铍原子的共价都是6．     

New binuclear vanadium(III) and (IV) squarate species: synthesis, structure and characterization of [V(OH)(H2O)2(C4O4)]2·2H2O and (NH4)[(VO)2(OH)(C4O4)2(H2O)3]·3H2O

Two new vanadium squarates have been synthesized, characterized by infrared and thermal behavior and their structures determined by single crystal X-ray diffraction. Both structures are made of discrete, binuclear vanadium entity but in 1, [V(OH)(H₂O)₂(C₄O₄)]₂·2H₂O the vanadium atom is trivalent and the entity is neutral while in 2, (NH₄)[(VO)₂(OH)(C₄O₄)₂(H₂O)₃]·3H₂O, the vanadium atom is tetravalent and the entity is negatively charged, balanced by the presence of one ammonium ion. Both molecular anions are bridged by two terminal μ₂ squarate ligands. 1 crystallizes in the triclinic system, space group P-1, with lattice constants a=7.5112(10) Å, b=7.5603(8) Å, c=8.2185(8) Å, α=106.904(8)°, β=94.510(10)°, γ=113.984(9)° while 2 crystallizes in the monoclinic system, space group C2/c, with a=14.9340(15) Å, b=6.4900(9) Å, c=17.9590(19) Å and β=97.927(12)°. From the magnetic point of view, V(III) binuclear species show ferromagnetic interactions at low temperatures. However, no anomalies pointing to magnetic ordering are observed down to 2 K.     

Structural study of Mn2(CO)8[P(NMe2)3]2

An X-ray crystal structure determination for the bimetallic complex Mn₂(CO)₈-[P(NMe₂)₃]₂ reveals that the P(NMe₂)₃ ligands are trans to the Mn---Mn bond and the Mn---Mn bond distance is relatively long, 2.946(1) Å.     

Reactivity of a functionalized trisamido ligand with Zr(NMe2)4 and GaMe3

NMR study of the reactivity of multifunctional ligand cis,cis-C₆H₉(NHCH₂C₆H₄-o-PPh₂)₃ (1) with GaMe₃ and Zr(NMe₂)₄ was carried out, yielding [cis,cis-(κ^N-NHCH₂C₆H₄-o-PPh₂)(κ^N-NCH₂C₆H₄-o-PPh₂)₂C₆H₉]GaMe (2) and [cis,cis-(NCH₂C₆H₄-o-PPh₂)₃C₆H₉]Ga₂Me₃ (3), and [cis,cis-(NCH₂C₆H₄-o-PPh₂)₃C₆H₉]Zr(NMe₂) (4), respectively. The spectral properties of 2 and 3 are very similar to that observed for the equivalent aluminum species already reported, but form at a much slower rate which allows for the observation of a GaMe₃⋅1 adduct. Species 4 undergoes coordination/displacement of one of the phosphine arms, which was observed using both NMR spectroscopy and DFT analyses.     

New octahedral Ta(V) hydrazido-substituted compounds for atomic layer deposition: Syntheses,X-ray diffraction structures of TaCl(NMe2)3[N(TMS)NMe2] and Ta(NMe2)4[N(TMS)NMe2], and fluxional behavior of the amido and hydrazido ligands in solution

The synthesis and structural characterization of new tantalum(V) compounds containing a single hydrazido(I) ligand are reported. Hydrazinolysis of TaCl(NMe₂)₄ using trimethylsilyl(dimethyl)hydrazine affords the compound TaCl(NMe₂)₃[N(TMS)NMe₂] in essentially quantitative yield. Metathetical replacement of the chloride ligand in TaCl(NMe₂)₃[N(TMS)NMe₂] by LiNMe₂ gives the all-nitrogen coordinated compound Ta(NMe₂)₄[N(TMS)NMe₂]. VT ¹H NMR studies support the existence of low-energy pathways involving rotation about the Ta–N bonds of the ancillary amido and hydrazido ligands in both hydrazido-substituted compounds. X-ray crystallographic analyses confirm the octahedral disposition about the tantalum metal in TaCl(NMe₂)₃[N(TMS)NMe₂] and Ta(NMe₂)₄[N(TMS)NMe₂] and the presence of an η²-hydrazido(I) ligand. Preliminary data using Ta(NMe₂)₄[N(TMS)NMe₂] as an ALD precursor for the preparation of tantalum nitride and tantalum oxide thin films are presented.     

[Co(en)3][In3(H2PO4)6(HPO4)3]·H2O: A new layered indium phosphate templated by cobalt complex

A new layered indium phosphate [Co(en)₃][In₃(H₂PO₄)₆(HPO₄)₃]·H₂O (1) has been synthesized solvothermally by using a racemic mix of chiral metal complex Co(en)₃Cl₃ as a template. Its structure is determined by single-crystal X-ray diffraction analysis and further characterized by X-ray powder diffraction, ICP, NMR and TG analyses. The inorganic layer is built up by alternation of In-centred octahedra (InO₆) and P-centered tetrahedra (PO₃(OH), PO₂(OH)₂, PO₂(=O)(OH) and PO(=O)(OH)₂) forming a 4.12-net. The metal complex cations locate in the interlayer region and interact with the host network through H-bonds. It is the first indium phosphate compound templated by a transition-metal complex and is isostructural with GaPO-CJ14. Crystal data: 1, monoclinic, space group P2₁/m (No. 11), a=9.1700(18) Å, b=22.6923(5) Å, c=9.9116(2) Å, β=107.87(3)°, Z=4, R_1[I>2σ(I)]=0.0287 and wR_{2(all data)}=0.0939.     

FeCo2(CO)7(μ3-S)(O[P(SCH2)2]2)的合成与晶体结构

许多化学工作者对单齿膦配体（ＰＰｈ３,ＰＢｕｎ３,ＰＥｔ２Ｐｈ,Ｐ（ＯＥｔ）３,Ｐ（ＯＣ６Ｈ５）３）与母体簇合物ＦｅＣｏ２（ＣＯ）９（μ３－Ｓ）的取代反应进行过详细研究［１－３］,但对双齿膦配体与母体簇合物的取代反应研究报导较少．Ａｉｍｅ［４］合成了含双齿膦配体的簇合物ＦｅＣｏ２（ＣＯ）７（μ３－Ｓ）（Ｐｈ２ＰＣＨ２ＰＰｈ２）,并用１３ＣＮＭＲ和ＩＲ光谱方法对其结构进行了表征．到目前为止,含双齿膦配体的该类簇合物的晶体与分子结构还未见报导．ＲｏｓａｎｎａＲｏｓｓｅｔｔｉ［２］通过研究母体簇合物与…     

Hydrothermal synthesis, crystal structure, and characterization of a new pseudo-two-dimensional uranyl oxyfluoride, [N(C2H5)4]2[(UO2)4(OH2)3F10]

A new uranyl oxyfluoride, [N(C₂H₅)₄]₂[(UO₂)₄(OH₂)₃F₁₀] has been synthesized by a hydrothermal reaction technique using (C₂H₅)₄NBr, UO₂(OCOCH₃)₂·2H₂O, and HF as reagents. The structure of [N(C₂H₅)₄]₂[(UO₂)₄(OH₂)₃F₁₀] has been determined by a single-crystal X-ray diffraction technique. [N(C₂H₅)₄]₂[(UO₂)₄(OH₂)₃F₁₀] crystallizes in the monoclinic space group P2₁/n (No. 14), with , , , β=98.88(3)°, , and Z=4. [N(C₂H₅)₄]₂[(UO₂)₄(OH₂)₃F₁₀] reveals a novel pseudo-two-dimensional crystal structure that is composed of UO₂F₅, UO₃F₄, and UO₄F₃ pentagonal bipyramids. Each uranyl pentagonal bipyramid shares edges and corners through F atoms to form a six-membered ring. The rings are further interconnected to generate infinite strips running along the b-axis. [N(C₂H₅)₄]₂[(UO₂)₄(OH₂)₃F₁₀] has been further characterized by elemental analysis, bond valence calculations, Infrared and Raman spectroscopy, and thermogravimetric analysis.     

[COH(NH2)2]2[Cu(pic)2(ClO4)2]的合成与晶体结构

The title compound was synthesized by reaction of Cu(ClO₄)₂， picolinic acid and carbamide in C₂H₅OH/CH₃CN solution， and characterized by single-crystal X-ray diffraction. It crystallizes in the orthorhombic system， space group Pbca with a=14.0481(8)， b=9.0130(5)， c=18.626(1)?， V=2358.3(2)?³， Z=4， D_x=1.771g·cm^-3， μ=1.235mm^-1 and F(000)=1276. The final R factor is 0.0440 for 1434 observed reflections. The X-ray analysis revealed that the copper(Ⅱ) atom is coordinated by two picolinic ligands in the equatorial plane， while the two oxygen atoms of perchlorate occupy the axial positions of octahedron with lengthened Cu-O distances， resulting in a 4+2 elongated octahedral environment. In the compound， there also exist two protonated carbamide cations for charge balance. CCDC： 195354.     

Synthesis and structures of bimetallic silicon-containing imido alkylidene complexes of tungsten (R′O)2(ArN)WCH-SiR2-CHW(NAr)(OR′)2 (R = Me, Ph) and (R′O)2(ArN)WCH-SiMe2SiMe2-CHW(NAr)(OR′)2

Bimetallic alkylidene complexes of tungsten (R′O)₂(ArN)WCH-SiR₂-CHW(NAr)(OR′)₂ (R = Me (1), Ph (2)) and (R′O)₂(ArN)WCH-SiMe₂SiMe₂-CHW(NAr)(OR′)₂ (3) (Ar = ; R′ = CMe₂CF₃) have been prepared by the reactions of divinyl silicon reagents R₂Si(CHCH₂)₂ with known alkylidene compounds R′′-CHMo(NAr)(OR′)₂. (R′′ = Bu^t, PhMe₂C) Complexes 1-3 were structurally characterized. Ring opening metathesis polymerization (ROMP) of cyclooctene using compounds 1-3 as initiators led to the formation of high molecular weight polyoctenamers with predominant trans-units content in the case of 1 and 3 and predominant cis-units content in the case of 2.     

Syntheses and crystal structures of [Mg(HF)2](SbF6)2 and [Ca(HF)2](SbF6)2: new examples of HF acting as a ligand to metal centres

[Mg(HF)₂](SbF₆)₂ and [Ca(HF)₂](SbF₆)₂ monocrystals were grown from the corresponding hexafluoroantimonates(V) dissolved in anhydrous hydrogen fluoride. [Mg(HF)₂](SbF₆)₂ crystallizes in the space group Pnma (no. 62) with a=1249.1(4) pm, b=1230.2(4) pm, c=699.1(2) pm, V=1.0742(6) nm³, Z=4. Magnesium is octahedrally coordinated by six fluorine atoms from which two belong to two HF molecules. The structure can be represented by alternating rows of magnesium and antimony atoms running parallel to the c-axis. Magnesium atoms are connected by cis bridging Sb(2)F₆ units along the a-axis and by trans bridging Sb(1)F₆ units along the b-axis. In this way a three-dimensional network is formed.[Ca(HF)₂](SbF₆)₂ crystallizes in the space group P2₁/n (no. 14) with a=935.2(3) pm, b=1088.7(3) pm, c=1104.8(3) pm, β=106.697(5)°, V=1.0774(5) nm³, Z=4. The coordination sphere around the calcium atom consists of eight fluorine atoms which define the vertices of an Archimedean antiprism. The two HF molecules directly coordinate the calcium atom and their fluorine atoms are placed in the corners of different square faces of the Archimedean antiprism. The Ca-F(HF) distances are shorter than the Ca-F(Sb) distances. The Sb(1)F₆ and Sb(2)F₆ groups have four equatorial bridging fluorine atoms, while the Sb(3)F₆ groups have only two bridging trans F ligands. The Ca atoms in the [−1,0,1] plane are connected by equatorial F ligands of Sb(1)F₆ and Sb(2)F₆ units, forming a [Ca(SbF₆)⁺]_n layer. These layers are connected by trans bridging Sb(3)F₆ groups. HF molecules occupy the space between these layers and additionally contribute to the connection between the layers by hydrogen bonding.     

Synthesis and characterization of organic-inorganic hybrid compounds with a pillared layer structure: Ga2(4,4′-bpy)(XO4)2 (X=P, As)

Two organic-inorganic hybrid compounds, Ga₂(4,4′-bpy)(PO₄)₂, 1, and Ga₂(4,4′-bpy)(AsO₄)₂, 2, have been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction. The two compounds are isostructural and crystallize in the triclinic space group (No. 2) with a=4.9723(9) Å, b=5.770(1) Å, c=11.812(2) Å, α=78.268(3)°, β=89.159(3)° γ=88.344(3)°, V=331.7(2) Å³, Z=1, and R1=0.0377 for 1, and a=5.1111(7) Å, b=5.9327(8) Å, c=11.788(2) Å, α=79.497(2)°, β=88.870(2)°, γ=88.784(2)°, V=351.3(2) Å³, and R1=0.0264 for 2. The structure consists of neutral sheets of GaXO₄ (X=P or As) which are pillared through 4,4′-bipyridine ligands. Each oxide layer, which is formed only by four-membered rings, is constructed from corner-sharing GaO₄N trigonal bipyramids and XO₄ tetrahedra. The title compounds are two of the few examples in which the gallium atoms are exclusively five-coordinate.     

Synthesis and crystal structure of Ru-supported tungstoantimonate [Sb2W20Ru2(H2O)2(dmso)6O68]

The first Ru^III-supported tungstoantimonate [Ru^II(bpy)₃]₂[Sb₂W₂₀Ru^III₂(H₂O)₂(dmso)₆O₆₈]·3dmso (bpy=bi-pyridine) (1a) has been successfully isolated as [Ru(bpy)₃]²⁺ (Rubpy) salt by routine synthetic reaction in mixed solutions with dmso and water. Single-crystal X-ray analysis was carried out on 1a, which crystallizes in the triclinic system space group P-1 with a=16.804 (6), b=16.988 (6), c=17.666 (6) Å, α=107.397 (13)°, β=106.883 (13)°, γ=103.616 (12)°. V=4309 (3) Å³, Z=1 with R1=0.0773. The compound 1a reveals the following features: (1) Rubpy is firstly used as an alternative ruthenium-source for the synthesis of Ru-substituted heteropolytungstate; (2) the structure of 1a consists of four Ru^III-O-S(CH₃)₂ and two W-O-S(CH₃)₂ bonds resulting in an assembly with C₂ symmetry; (3) the Ru^III ions are linked to two dmso groups via two Ru^III-O-S(CH₃)₂ bonds, which represents the other dmso-coordination mode to Ru^III in POM chemistry. The cyclic voltammetry studies of 1a in dmso/H₂SO₄ (3/1 v/v) at pH 2.5 medium using the glassy carbon electrode as a working electrode show the respective electrochemical behaviors of the W-centers and the Ru-centers within 1a, which could be separated clearly. In addition, the compound 1a exhibits photoluminescence arising from π*−t_2g ligand-to-metal transition of Rubpy.     

Bis(trifluoromethyltellurato(0))metallates(I) of copper, silver and gold, [M(TeCF3)2] (M = Cu, Ag, Au)

Ligand exchange reactions of [NMe₄]TeCF₃ and CuBr, Ag[BF₄] and AuCl have been studied in molar ratios of 2:1. While evidence is found for [Cu(TeCF₃)₂]⁻ moieties by ¹⁹F-NMR spectroscopic and mass spectrometric means, [NMe₄][Ag(TeCF₃)₂] and [NMe₄][Au(TeCF₃)₂] were isolated. After cation exchange, the latter compounds were fully characterised as the [PNP] salts ([PNP] = bis(triphenylphosphoranylidene)ammonium). The single crystal structure of [PNP][Au(TeCF₃)₂] has been elucidated by XRD measurements (P2₁/a; a = 1765.6(1), b = 1126.0(1), c = 2055.2(1) pm; β = 111.98(1)°; Z = 4).     

Syntheses and X-ray crystallographic studies of {[Ni(en)2(pot)2]0.5CHCl3} and [Ni(en)2](3-pytol)2

Two novel Ni(II) complexes {[Ni(en)₂(pot)₂]0.5CHCl₃} (3) {pot = 5-phenyl-1,3,4-oxadiazole-2-thione} (1) and [Ni(en)₂](3-pytol)₂ (4) {3-pytol = 5-(3-pyridyl)-1,3,4-oxadiazole-2-thiol} (2) have been synthesized using en as coligand. The metal complexes have been characterized by physical and analytical techniques and also by single crystal X-ray studies. The complexes 3 and 4 crystallize in monoclinic system with space group P21/a and P121/c, respectively. The complex 3 has a slightly distorted octahedral geometry with trans (pot)⁻ ligands while 4 has a square planar geometry around the centrosymmetric Ni(II) center with ionically linked trans (3-pytol)⁻ ligands. The π?π (face to face) interaction plays an important role along with hydrogen bondings to form supramolecular architecture in both complexes.     

Tetramethylammonium trifluoromethyltellurate(0), [NMe4]TeCF3, synthesis, characterisation and properties

[NMe₄]TeCF₃ is obtained in 60% yield from Me₃SiCF₃, elemental tellurium and [NMe₄]F in glyme as a pale yellow solid decomposing at 185 °C. Cation exchange with [PNP]Br ([PNP] = bis(triphenylphosphoranylidene)ammonium) and [(dibenzo-18-crown-6)K]Br occurs spontaneously. These low co-ordinating cations increase significantly the nucleophilicity of the anion.