具有新结构类型的化合物Csln[PO3(OH)]2的合成与结构

水热法合成了新结构类型化合物CsIn[P03(0H)]2,并通过单晶X-射线衍射表征结构.标题化合物空间群为P121/c1(No.14),晶体学参数为:M=439.69,mP56,a=0.532 86(6)nm,b=0.91653(7)nm,c=1.478 39(14)nm,β=93.849(9).,V=0.7204(1)nm3,Z=4,Dx=4.054 g·cm-3,μ=8.713 mm-1,F(000)=800,R1= 0.0325,wR2=0.0874.在该化合物中,2个In06八面体和4个PO4四面体形成交连的六元环柱,并沿a轴方向形成近六方密堆积并连接成Cs+离子占据的十二元环结构隧道,六元环和十二元环连接构筑了三维网络结构.与类似化学计量比化合物Na2In2[PO3(0H)]4·H2O比较,标题化合物中十二元环的形成明显取决于隧道阳离子的大小,其拓扑构造可看作扩展的6,3-网格连接,化合物RbIn[PO3(0H)]2与之同构.     

[HN(C2H5)3][B5O6(OH)4]的合成、结构和热稳定性

利用水热法合成了五硼酸三乙胺[HN(C2H5)3][B5O6(OH)4], 并利用单晶X射线衍射技术解析了其结构, 同时利用傅立叶红外分析、元素分析及热分析技术加以佐证. 该化合物属于单斜晶系, 其空间群为P21/c, 相应的晶胞参数为a=1.0036(2) nm, b=1.1353(2) nm, c=1.4843(3) nm和β=106.54(3)°. 它由孤立的五硼酸阴离子[B5O6(OH)4]-和三乙胺阳离子[HN(C2H5)3]+构成. 五硼酸阴离子[B5O6(OH)4]-通过氢键构成三维网状结构, [HN(C2H5)3]+位于其中的孔道中.     

[Pb(3-HPYA)2]n的合成及其晶体结构

3-(3-吡啶基)丙烯酸(3-HPYA)配体与过渡金属离子铅通过水热法合成了一种新的三维配位聚合物[Pb(3-HPYA)2]n(1),其结构经IR,元素分析和X-射线单晶衍射仪表征.1属于单斜晶系,空间群P2/c,晶胞参数:a=1.032 3(3)nm,b=1.6944(5)nm,c=0.864 9(3)nm,β=93.939(5)°,Z=1.509 2(8)nm3,Z=4,Mr=490.73,Dc=2.216 g·cm-3,F(000)=9444,μ=11.200.     

一种新的16金属笼状物[HN(C2H5)3]4-[MoV3MoVI6VIV7O40(PO4)]·2[N(C2H5)3]的水热合成和结构

报道了一种新的杂多化合物[HN(C2H5)3]4[MoV3MoVI6VIV7O40(PO4)](2[N(C2H5)3]的合成, 并用元素分析、EPR、IR谱、及X--射线单晶衍射等手段进行了表征.结果表明, 该杂多酸盐属于单斜晶系, 空间群P21/n, a = 14.0841(3), b = 14.2505(3), c = 19.6089(3) A,β= 94.213(1)°, V = 3925.0(1)A3, Z = 2, Dc = 2.171 g/cm3, Mr = 2566.18, μ = 2.284 mm-1, F(000) = 2516, R = 0.0477, Wr = 0.0945. 杂多阴离子是1个16金属笼状物, 笼中心包含1个PO4四面体客体.     

Mo-Ag类立方烷异四核簇[Mo~2Ag~2S~4](TDT)~2(PPh~3)~2的合成, 结构表征和反应性

采用[2 1 1]的设计合成模式,以二核化合物[Mo_2S_4(TDT)_2](Me_4N)_2(1,TDT=S_2C_6H_3CH_3~(2-))为起始物,与Ag(PPh_3)_3(NO_3)反应,首次合成[Mo_2Ag_2S_4](TDT)_2(PPh_3)_2CH_2Cl_2(2)的类立方烷异四核簇合物.文中报道了该化合物的晶体结构、红外光谱、紫外可见光谱和电化学研究结果,以此簇合物和过量的Cu(PPh_3)_2dtP[dtP=S_2P(OEt)_2]反应发现金属Ag可被Cu取代,形成其同系物[Mo_2Cu_2S_4](TDT)_2(PPh_3)_2,这是迄今研究较少的原子簇反应类型.化合物的结晶学参数如下:单斜晶系,空间群:P2_1/n,晶胞参数:a=1.7202(4)nm,b=1.7632(3)nm,c=1.9033(8)nm,β=99.24(3)°,V=5.698(3)nm~3,Z=4,D_c=1.69g/cm~3,对于6158个衍射,最终结构偏离因子R=0.040,R_W=0.048.     

具有新结构类型的化合物CsIn[PO_3(OH)]_2的合成与结构(英文)

水热法合成了新结构类型化合物CsIn[PO3(OH)]2,并通过单晶X--射线衍射表征结构。标题化合物空间群为P121/c1(No.14),晶体学参数为:Mr=439.69,mP56,a=0.53286(6)nm,b=0.91653(7)nm,c=1.47839(14)nm,β=93.849(9)°,V=0.7204(1)nm3,Z=4,Dx=4.054g·cm-3,μ=8.713mm-1,F(000)=800,R1=0.0325,wR2=0.0874。在该化合物中,2个InO6八面体和4个PO4四面体形成交连的六元环柱,并沿a轴方向形成近六方密堆积并连接成Cs 离子占据的十二元环结构隧道,六元环和十二元环连接构筑了三维网络结构。与类似化学计量比化合物Na2In2[PO3(OH)]4·H2O比较,标题化合物中十二元环的形成明显取决于隧道阳离子的大小,其拓扑构造可看作扩展的6,3-网格连接,化合物RbIn[PO3(OH)]2与之同构。     

[C0(Im)6]·(CF3COO)2配合物的晶体结构和光谱性质

合成了一种新的配合物[Co(Im)6]·(CF3COO)2(Im=Imidazole),并用X射线衍射分析、核磁共振氢谱和红外光谱对其结构进行了表征.结果表明,该配合物属于单斜晶系,空间群为P21/c,晶胞参数为α=1.086 3(2)nm,b=1.779 0(4)nm,c=0.789 38(16)nm,α=90°,β...     

Mo-Ag类立方烷异四核簇[Mo~2Ag~2S~4](TDT)~2(PPh~3)~2的合成, 结构表征和反应性

采用[2+1+1]的设计合成模式, 以二核化合物[Mo~2S~4(TDT)~2](Me~4N)~2(1,TDT=S~2C~6H~3CH~3^2^-)为起始物,与Ag(PPh~3)~3(NO~3)反应,首次合成[Mo~2Ag~2S~4](TDT)~2(PPh~3)~2·CH~2Cl~2(2)的类立方烷异四核簇合物.文中报道了该化合物的晶体结构,红外光谱,紫外可见光谱和电化学研究结果, 以此簇合物和过量的Cu(PPh~3)~2dtp[dtp=S~2P(OEt)~2]反应发现金属Ag可被Cu取代,形成其同系物[Mo~2Cu~2S~4](TDT)~2(PPh~3)~2.这是迄今研究较少的原子簇反应类型.化合物的结晶学参数如下:单斜晶系,空间群:P2~1/n,晶胞参数:a=1.7202(4)nm,b=1.7632(3)nm,c=1.9033(8)nm.β=99.24(3)°,V=5.698(3)nm^3,Z=4,D~c=1.69g/cm^3.对于6158个衍射,最终结构偏离因子R=0.040,R~W=0.048     

三维超分子化合物[Mn(phen)3 ]2(H3O)O40 ]·2H2 O的水热合成与结构表征

利用水热合成方法制备了Keggin结构多金属氧酸盐[Mn(phen)3]2(H3O)·2H2O,用元素分析、红外光谱、热分析和X射线单晶衍射测试技术对其结构进行了表征. 结果表明,该化合物属于单斜晶系,C2/c空间群,a=2.728 5(3) nm,b=2.506 0(3) nm,c=1.633 6(18) nm,β=104.911(2)°,V=10.79 4(2) nm3,Z=4,R1=0.078 4,wR2=0.199 9. 化合物分子结构单元由1个Keggin结构多金属氧酸盐阴离子5-,2个配位阳离子[Mn(phen)3]2+,1个质子和2个结晶水分子构成. 化合物分子之间通过π-π堆积作用形成了三维超分子结构.     

CRYSTAL STRUCTURE OF [Mo_3S_4 (μ-CH_3COO) [S_2P(OEt)_2]_3 (py)] (CH_3COOCH_2CH_3)

<正> [Mo3S4(μ-CH3COO)[S2P(OEt)2]3(py)]·(CH3COOCH2CH3) , Mr = 1197. 96,monoclinic,P21/n,a=13. 158(2),b=23. 153(5), c=16. 175(3) A,β = 112. 79(1)°,V=4543. 1(7)A3,Z=4, Dc= 1. 751g/cm-3,λ(MoKa) = 0. 71073A ,μ= 13. 799cm-1,F(000) = 2408. Final R=0. 067 for 4000 reflections. The structure consists of the neutral cluster molecule [Mo3S4(μ-OAc) (dtp)3(py)] (dtp = [S2P(OEt)2]) and the solvent ethyl acetate (AcOEt). The three Mo-Mo bond lengths in the title compound are 2. 691(2) ,2. 747(2) ,2. 762(2) A ,whereas the Mo-N bond length in Mo(3) position is 2. 36(2)A. The important bond lengths of these Mo clusters with (py) ring at the loose coordination site are listed for comparison.     

[Cu(en)2]0.5[Al3P3O12(OH)]-aluminophosphate with zeotype AWO: Synthesis, crystal structure and phase transformation

A new aluminophosphate [Cu(en)₂]_0.5[Al₃P₃O₁₂(OH)] (denoted as AlPO-CJ53; en = ethylenediamine) with zeotype AWO topology has been synthesized under hydrothermal conditions in which the self-assembled Cu(en) ₂ ²⁺ cations in the reaction system act as the template. AlPO-CJ53 crystallizes in the monoclinic space group P2₁/n (No. 14) with a = 0.85547(11) nm, b = 1.7671(2) nm, c = 0.90500(12) nm, β = 107.725(2)°, V = 1.3031(3) nm³. Its framework consists of AlO₄(OH)/AlO₄ and PO₄ units forming 8-ring channels along the c direction, where the copper complex cations Cu(en) ₂ ²⁺ are located to neutralize the negative charges of the framework. AlPO-CJ53 transforms to AlPO₄-25 with zeotype ATV upon calcination at 400 °C.     

The First Examples of Selenidogermanate Salts with Lanthanide Complex Counter Cations: Solvothermal Syntheses and Characterizations of [{Ln(en)3}2(μ‐OH)2]Ge2Se6 (Ln = Eu,Ho) and [{Ho(dien)2}2(μ‐OH)2]Ge2Se6

The lanthanide selenidogermanates [{Eu(en)₃}₂(μ‐OH)₂]Ge₂Se₆ ( 1 ), [{Ho(en)₃}₂(μ‐OH)₂]Ge₂Se₆ ( 2 ), and [{Ho(dien)₂}₂(μ‐OH)₂]Ge₂Se₆ ( 3 ) (en = ethylenediamine, dien = diethylenetriamine) were solvothermally prepared by the reactions of Eu₂O₃ (or Ho₂O₃), germanium, and selenium in en and dien solvents respectively. Compounds 1 – 3 are composed of selenidogermanate [Ge₂Se₆]^4– anion and dinuclear lanthanide complex cation [{Ln(en)₃}₂(μ‐OH)₂]⁴⁺ (Ln = Eu, Ho) or [{Ho(dien)₂}₂(μ‐OH)₂]⁴⁺. The [Ge₂Se₆]^4– anion is composed of two GeSe₄ tetrahedra sharing a common edge. The dinuclear lanthanide complex cations are built up from two [Ln(en)₃]³⁺ or [Ho(dien)₂]³⁺ ions joined by two μ‐OH bridges. All lanthanide(III) ions are in eight‐coordinate environments forming distorted bicapped trigonal prisms. In 1 – 3 , three‐dimensional supramolecular networks of the anions and cations are formed by N–H ··· Se and N–H ··· O hydrogen bonds. To the best of our knowledge, 1 – 3 are the first examples of selenidogermanate salts with lanthanide complex counter cations.     

[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,Crystal Structure,and Hydrogen Bonding of μ‐Hydroxo‐μ‐peroxo‐bis[bis(ethylenediamine)cobalt(III)] Squarate

Black‐brown needle‐shaped single crystals of [Co₂(en)₄(O₂)(OH)][C₄O₄]_1.5 · 4H₂O (en = ethylenediamine) were prepared in aqueous solution at room temperature [space group P$\bar{1}$ (no.2) with a = 800.20(8), b = 1225.48(7), c = 1403.84(9) pm, α = 100.282(5), β = 94.515(7), and γ = 95.596(6)°]. The Co³⁺ cations [Co(1), Co(2)] are coordinated in an octahedral manner by four nitrogen atoms stemming from the ethylenediamine molecules and two oxygen atoms each from a hydroxo group and a peroxo group, respectively. Both Co³⁺ coordination polyhedra are connected by a common corner and by the peroxo group leading to the dinuclear [(en)₂Co(O₂)(OH)Co(en)₂]³⁺ cation. The squarate dianions, not bonded to Co³⁺, and the [(en)₂Co(O₂)(OH)Co(en)₂]³⁺ cations are linked by hydrogen bonds forming a three‐dimensional supramolecular network containing water molecules. Magnetic measurements revealed a diamagnetic behavior indicating a low‐spin electron configuration of Co³⁺. The UV/Vis spectra show two LMCT bands [π*(O₂^2–) → d_σ*(Co³⁺)] at 274 and 368 nm and the d–d transition (¹A_1g → ¹T_1g) at 542 nm. Thermoanalytical investigations in air show that the compound is stable up to 120 °C. Subsequent decomposition processes to cobalt oxide are finished at 460 °C.     

A new cyanobridged one-dimensional coordination polymer based on the octahedral rhenium cluster [Re6Se8(CN)6]4−: Synthesis and crystal structure of [{Cu(H2O)0.5(en)2} {Cu(en)2}Re6Se8(CN)6]·3H2O

The rhenium cluster complex [{Cu(H₂O)_0.5(en)₂} {Cu(en)₂} Re₆Se₈(CN)₆]·3H₂O has been obtained by the reaction of an aqueous solution of K₄[Re₆Se₈(CN)₆]·3.5H₂O with an aqueous solution of Cu(en)₂Cl₂ using cross diffusion through a gel. The structure of the compound has been characterized by a single-crystal X-ray diffraction method (a = 10.690(3) Å, b = 15.035(5) Å, c = 25.847(8) Å, V = 4154(2) ų, Z = 4, space group P2₁2₁2₁, R = 0.0651). Cluster anions [Re₆Se₈(CN)₆]^4? in the complex are connected with Cu²⁺ cations by cyano bridges resulting in zigzag chains. Coordination environment of cations is completed by ethylenediamine molecules. Additionally each cluster anion is coordinated by one terminal fragment {Cu(H₂O)_0.5(en)₂}.     

Potentiometric and spectrophotometric titration of Cu2+ complexes with N-isopropyl-2-methyl-1,2-propanediamine

The complexation of Cu²⁺ by N-isopropyl-2-methyl-1,2-propanediamine (L) has been studied by potentiometric and spectrophotometric titration. The dominant complexes formed in this system are [CuL]²⁺, [CuL₂]²⁺, [Cu₂L₂(OH)₂]²⁺, and [CuL(OH)₂]. The data were thoroughly tested for different models with [CuL(OH)]⁺, [CuL(OH)]⁺, [Cu(OH)]⁺, and [Cu₂(OH)₂]²⁺ as additional species. The importance of steric factors is indicated by the d-d* spectra: for [CuL₂]²⁺, (λ_max = 499 nm) the absorption maximum is shifted by 50 nm to high energies relative to [Cu(en)₂]²⁺, (λ_max = 549 nm), whereas the opposite is true for the 1:1 complexes ([CuL]²⁺ : λ_max = 712 nm,s [Cu(en)]²⁺ : λ_max = 660 nm).     

Co(en)3[B4O5(OH)4]Cl·3H2O和[Ni(en)3][B5O6(OH)4]2·2H2O的合成、结构以及热力学性质

利用水热法合成了两种过渡金属配合物为模板剂的含水硼酸盐晶体Co(en)3[B4O5(OH)4]Cl·3H2O(1) 和 [Ni(en)3][B5O6(OH)4]2·2H2O (2),并通过元素分析、X射线单晶衍射、红外光谱及热重分析对其进行了表征。化合物1晶体结构的主要特点是在所有组成Co(en)33+, [B4O5(OH)4]2–, Cl– 和 H2O之间通过O–H…O、O–H…Cl、N–H…Cl和N–H…O四种氢键连接形成网状超分子结构。化合物2晶体结构的特点是[B5O6(OH)4]–阴离子通过O–H…O氢键连接形成沿a方向有较大通道的三维超分子骨架,模板剂[Ni(en)3]2+阳离子和结晶水分子填充在通道中。     

A New Organic‐Inorganic Hybrid Copper Pentaborate with Free Boric Acid Group

The hydrothermal reaction of Cu(CH₃COO)₂·H₂O, H₃BO₃, ethylenediamine and H₂O in a molar ratio of 3:20:9:222 at 140°C for 5 d yields the deep blue crystals of a new copper polyborate [Cu(en)₂B(OH)₃]· [B₅O₅(OH)₇] (en?H₂NCH₂CH₂NH₂) in 70% yield. It crystallizes in monoclinic system, space group P2₁/c, with unit cell dimensions, a=1.2779(2) nm, b=1.0167(15) nm, c=1.5019(2) nm, β=90.30(2)°, Z=4. The crystal structure of this compound consists of [Cu(en)₂B(OH)₃]²⁺ cation and [B₅O₅(OH)₇]^2? anion, which are linked together through hydrogen bonding interactions and electrostatic forces, forming an interesting three‐dimensional framework. The [B₅O₅(OH)₇]^2? anion is constituted of [B₄O₅(OH)₄]^2? anion and discrete B(OH)₃ group which attaches to the side of [B₄O₅(OH)₄]^2? through intramolecular hydrogen bonds. Fundamental vibrational modes of this compound were identified and band assignments were made. The middle bands observed at 882 and 575 cm^?1 in Raman spectrum are the characteristic peak of B(OH)₃ group and [B₄O₅(OH)₄]^2? anion, respectively. Additionally the thermal behavior of title compound was recorded and its decomposition mechanism was discussed.     

Hydrate isomerism in [Cu(en)2(H2O)1.935]2[Fe(CN)6]·4H2O

The title compound, bis[di­aqua­bis­(ethyl­enedi­amine‐κ²N,N′)copper(II)­] hexa­cyano­iron(II) tetrahydrate, [Cu(C₂H₈N₂)₂(H₂O)_1.935]₂[Fe(CN)₆]·4H₂O, was crystallized from an aqueous reaction mixture initially containing CuSO₄, K₃[Fe(CN)₆] and ethyl­enedi­amine (en) in a 3:2:6 molar ratio. Its structure is ionic and is built up of two crystallographically different cations, viz. [Cu(en)₂(H₂O)₂]²⁺ and [Cu(en)₂(H₂O)_1.87]²⁺, there being a deficiency of aqua ligands in the latter, [Fe(CN)₆]⁴⁻ anions and disordered solvent water mol­ecules. All the metal atoms lie on centres of inversion. The Cu atom is octahedrally coordinated by two chelate‐bonded en mol­ecules [mean Cu—N = 2.016 (2) Å] in the equatorial plane, and by axial aqua ligands, showing very long distances due to the Jahn–Teller effect [mean Cu—O = 2.611 (2) Å]. In one of the cations, significant underoccupation of the O‐atom site is observed, correlated with the appearance of a non‐coordinated water mol­ecule. This is interpreted as the partial contribution of a hydrate isomer. The [Fe(CN)₆]⁴⁻ anions form quite regular octahedra, with a mean Fe—C distance of 1.913 (2) Å. The dominant intermolecular interactions are cation–anion O—H⋯N hydrogen bonds and these inter­actions form layers parallel to (001).     

Solvothermal synthesis and crystal structure of Sb(III) and Sb(V) thioantimonates: [Mn(en)3]2Sb2S5 and [Ni(en)3(Hen)]SbS4

Thioantimonate compounds of [Mn(en)₃]₂Sb₂S₅ (1) and [Ni(en)₃(Hen)]SbS₄ (2) (en=ethylenediamine) were prepared by reaction of transition metal chloride with Sb and S₈ powders under solvothermal conditions. Compound 1 consists of discrete [Sb₂S₅]⁴⁻ anion, which is formed by corner-sharing SbS₃ trigonal pyramids. Compound 2 is composed of discrete tetrahedral [SbS₄]³⁻ anion. The compounds 1 and 2 are charge compensated by [M(en)₃]²⁺ cations, whereas in the crystal of 2 there is another counter ion of [Hen]⁺. The results of the synthesis suggest that the temperature, the concentration and the existing states of the starting materials and so on are important for the structure and composition of the final products. In addition, the oxidation-state of antimony might be related to the molar ratio of the reactants. Excess amount of elemental S is beneficial to the higher oxidation-state of thioantimonate (V). Compound 1 decomposes from 150°C to 350°C, while compound 2 decomposes from 200°C to 350°C remaining Sb₂S₃ and NiSbS as residues.