[C4N2H12]1.5[Zn2(PO4)(HPO4)2]·H2O晶体的合成与表征

由于在电学、磁学、光学、吸附、离子交换和催化等领域具有潜在的应用价值,具有开放骨架结构的金属磷酸盐的合成一直受到人们的广泛关注。在这些磷酸盐微孔化合物中,磷酸锌晶体是拓扑结构最为丰富的一种犤1犦。自从Stucky等犤2犦报道具有SOD、Li-ABW、FAU等已知结构磷酸锌的合成以来,已经有近百种具有0-D犤3,4犦,1-D犤5,6犦,2-D犤7～9犦,3-D犤10～13犦结构的磷酸锌被成功地合成出来。其中令人瞩目的是具有螺旋孔道的手性磷酸锌犤14犦以及具有二十四元环孔道的两种微孔磷酸锌化合物犤15,16犦的合成。这些化合物大多是采用水热技术以有…     

新型层状氟化磷酸铝[C4H12N2][Al2(PO4)2(H2O)2F2]的水热合成与表征

自从1982年Wilson等发现一类新型微孔材料磷酸铝分子筛(AlPO4-n)以来,大量具有新颖结构的磷酸铝化合物被合成出来,它们在催化、离子交换、吸附和主-客体组装等方面均具有潜在的应用前景,这类化合物大多是在水热或溶剂热体系中和有机模板剂存在条件下合成的,1978年,Flanigen等首先在反应体系中加入氟离子作矿化剂合成了硅晶体,后来,氟离子方法在硅铝体系和金属磷酸盐体系中也得到了广泛的应用,氟离子在反应过程中起到矿化剂或结构导向剂的作用,     

Synthesis,Crystal Structure,and Characterization of A New Adduct Bis-(2-Amino-3-Benzyloxypyridinium) Selenate Monohydrate [C12H13N2O]2SeO4.H2O

Abstract

A new adduct bis-(2-amino-3-benzyloxypyridinium) selenate monohydrate, [C₁₂H₁₃N₂O]₂SeO₄.H₂O, has been synthesized by slow evaporation at room temperature using 2-amino-3-benzyloxypyridine as the structure-directing agent. The structure, determined by single-crystal X-ray diffraction at 298 K, can be described as organic-inorganic tunnels with different forms built by infinite inorganic chains parallel to the c axis and connected to the organic cations. In this atomic arrangement, hydrogen bonds and van der Waals interactions between the different species play an important role in the tri-dimensional network cohesion. Solid-state ¹³C and ⁷⁷Se MAS NMR spectroscopy results are in agreement with the X-ray structure.

[Supplementary materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfer, and Silicon and the Related Elements for the following free supplemental files: Additional figures and tables.]     

以哌嗪为模板剂的二维层状硫酸铈[C4N2H12]3[Ce2(SO4)6(H2O)2]·H2O的水热合成与晶体结构表征

以哌嗪为模板剂, 在水热条件下合成了一个新的具有二维拓展骨架结构的稀土硫酸盐[C4N2H12]3[Ce2(SO4)6(H2O)2]·H2O, 并对其进行了结构表征和热分析. 单晶结构解析结果表明, 该化合物晶体属于单斜晶系, P21/c空间群, 晶体学参数a=0.66335(10) nm, b=2.8088(4) nm, c=1.02212(15) nm, β=96.160(2)°, V=1.8935(5) nm3, R1=0.0466, wR2=0.1226. 该化合物由[—Ce—S3—Ce—S1—Ce— S3—Ce—S1—]八元环连接形成二维层状结构, 无机层间通过氢键连接成三维无限结构.     

新型磷-钒-氧层状化合物[H2en]2[H3O]6[Co(H2O)2(VO)8(OH)4(PO4)8]的水热合成与晶体结构

金属磷酸盐材料在吸附、离子交换、离子传导和催化剂方面有潜在的应用前景[1～5]. 近年来, 通过水热反应合成了一些A-V-P-O化合物. 在这些化合物中, A一般为碱金属或有机阳离子, 如层状结构的[H2N(C4H8)2NH2][(VO)4(OH)4(PO4)2][6] 和[H2N(C2H4)3NH2][(VO)8(HPO4)3(PO4)4*(OH)2]*2H2O[6], 一维链状结构的 [H2NCH2CH2NH3(VO)(PO4)][7], 手性双螺旋结构的 [(CH3)2NH2]K4[(VO)10(H2O)2(OH)4(PO4)7]*H2O[8]以及具有三维骨架结构的化合物 [H3N(CH2)3NH3K(VO)3(PO4)3][9], [H3N(CH2)3NH3]2[V(H2O)2(VO)6(OH)2(HPO4)3(PO4)5]*3H2O[10]和[H3N(CH2)2NH3][(VO)3(H2O)2(PO4)2(HPO4)4][11].     

Synthesis,Crystal Structure,and Characterization of a New Adduct 3-Ammoniumphenyl Sulfone Dihydrogenphosphate Phosphoric Acid [C12H14N2SO2](H2PO4)2H3PO4

Abstract

A new adduct 3-ammoniumphenyl sulfone dihydrogenphosphate phosphoric acid, [C₁₂H₁₄N₂O₂S](H₂PO₄)₂H₃PO₄, has been synthesized by slow evaporation at room temperature using 3-aminophenyl sulfone as the structure-directing agent. The structure, determined by single-crystal X-ray diffraction at 293 K, can be described as inorganic layers built by H₂PO₄ ^? groups and H₃PO₄ molecules, parallel to the (a, c) planes at y = 0.5, between which molecules of the organic group [C₁₂H₁₄N₂O₂S]²⁺ are inserted. In this atomic arrangement, hydrogen bonds and van der Waals interactions between the different species play an important role in the tri-dimensional network cohesion. Solid-state ¹³C and ³¹P MAS NMR spectroscopies are in agreement with the X-ray structure.

[Supplemental materials are available for this article. Go to the publisher's online edition of Phosphorus, Sulfur, and Silicon and the Related Elements for the following free supplemental resource: Tables S1 and S2. Figures S1 and S2.]

GRAPHICAL ABSTRACT      

[C6N2H18]2[Mo5O15(HPO4)2]·H2O的水热合成与结构表征

通过水热法合成了一个新化合物[C6N2H18]2[Mo5O15(HPO4)2]·H2O,并通过IR光谱、ICP、元素分析、差热与热重分析和X射线单晶衍射分析等手段进行了表征.结果表明,晶体属三方晶系,P3(2)21空间群,a=1.1231(1)nm,c=2.2802(5)nm,V=2.4911(7)nm3,Dx=2.835Mg/m3,Z=6,最后的一致性因子R=0.0227,wR=0.0675.阴离子中Mo5O15构成一环状结构,2个HPO4一个连在环的下方,一个连在环的上方,形成类似于“飞碟”状的结构,阳离子为2个质子化的四甲基乙二胺.     

Hydrothermal Syntheses and Structural Characterization of One-Dimensional [Cu4Br2I3(C12H8N2)2] n and Molecular Cu3Br3(C12H8N2)2

The hydrothermal reactions of CuBr₂, CuX (X=Br, I), and phen (phen=1,10-phenanthroline, C₁₂H₈N₂) have lead to the syntheses of two novel complexes of one-dimensional [Cu₄Br₂I₃(phen)₂] _n 1 and trinuclear discrete cluster Cu₃Br₃(phen)₂ 2. Both compounds were characterized by singe-crystal X-ray diffraction. Crystal data for 1. Monoclinic, space group P2 ₁/c with a=14.054(3) Å, b=13.700(3) Å, c=15.920(3) Å, =114.16(3)°, Z=2; 2. Monoclinic, space group C2/c with a=10.040(2) Å, b=14.516(3) Å, c=16.319(3) Å, =94.29(3)°, Z=6.     

新的四帽Keggin结构的金属-氧簇合物[NiMo12O40H10{Ni(H2O)3}4]的水热合成与结构表征

多金属氧酸盐 (也称金属 -氧簇 )由于在催化、材料及医药等领域的应用日益广泛而备受关注 .近年来 ,一些新颖的非经典结构的化合物不断被合成出来 .如带二帽的 Keggin结构化合物 [V15O4 2 ]9- [1] ,[PV14 O4 2 ]9- [2 ] ,[As V14 O4 2 ]9- [3 ] ,[{ Mo8V7O4 2 } 2 ]14 - [4 ] ,     

3D Coordination Polymers with Chiral Structures, [Ln2(tda)2(H2O)3]·5H2O: Hydrothermal Synthesis,Structural Characterization,and Luminescent Properties

Reactions of H₃tda (H₃tda = 1H‐1, 2, 3‐triazole‐4, 5‐dicarboxylic acid) with Sm(NO₃)₃ · 6H₂O, Eu(NO₃)₃ · 6H₂O, and Tb(NO₃)₃ · 6H₂O, in the presence of NaOH under hydrothermal conditions, produced three new coordination polymers, [Ln₂(tda)₂(H₂O)₃] · 5H₂O [Ln = Sm ( 1 ), Eu ( 2 ), Tb ( 3 )]. These compounds were structurally characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis (TGA), PXRD and single‐crystal X‐ray diffraction. The single‐crystal X‐ray diffraction studies of compounds 1 – 3 reveal that all compounds are three‐dimensional porous structures with chiral frameworks. Furthermore, the luminescence studies of compound 2 and 3 in the solid state reveal that they are potential luminescent materials at room temperature.     

Hydrothermal Synthesis and Structure Characterization of Open-framework Cobalt-tungsten Phosphate[H3NCH2CH2NH3]3[Co3W4P4O28]

A new three-dimensional open-framework cobalt(Ⅱ)-tungsten(Ⅵ) phosphate,[H3NCH2CH2NH3]3·[Co3W4P4O28](1) has been synthesized from the reaction of CoCl2·6H2O,WO3,H3PO4,ethylenediamine and H2O.The title compound was fully characterized by infrared spectroscopy,elemental analysis,magnetic properties,thermogravimetric analysis,XPS and single-crystal X-ray diffraction.The compound crystallized in a tetragonal space group I4(1)/a with a=1.7118(4) nm,c=1.0773(2) nm,V =3.1568(11) nm3,Z =4.     

新型杂多化合物[(CH3CH2)4N]4H3O· {Na[(HMo2O5)3(HPO4)(H2PO4)3]2}·(H2PO4)2·10H2O的水热合成与晶体结构

杂多化合物在催化、医药、材料及光化学等方面具有广泛的应用前景 [1～ 4 ] ,其中钼磷多金属氧酸盐具有优异的氧化催化性能 [5,6 ] .近年来合成的新奇结构的钼磷多金属氧酸盐中已测定结构的有含帽[7,8] 和非帽[9～ 12 ] 系列 .本文利用水热法合成了未见文献报道的结构新颖的夹心型磷钼多金属氧酸盐[( CH3CH2 ) 4N]4 H3O{Na[( HMo2 O5) 3( HPO4 ) ( H2 PO4 ) 3]2 }· ( H2 PO4 ) 2 · 1 0 H2 O,并测定了其晶体结构 .1　实验与晶体结构分析1 .1　仪器与试剂　元素 Na用美国原子吸收分光光度计测定 ;C,H和 N用 Perkin- Elmer 2 4 0…     

Hydrothermal Synthesis and Crystal Structure of a Novel Polyoxometalate K（C4N2H12）4（C4N2H11）2- [Mo8^VMo4^（VI）CdP8O54（OH）8]F·6H2O

The title compound 1 has been synthesized by the reaction of H2MoO4,CdCl2,H3PO4,KF,piperazine hexahydrate and water in aqueous solution under mild hydrothermal conditions. Single-crystal X-ray analysis reveals that the title compound crystallizes in the triclinic system,space group P1 with a = 14.049（3）,b = 15.972（3）,c = 20.043（4） A,α = 85.82（3）,β = 81.28（3）,γ = 67.15（3）°,V = 4095.9（14） A^3,Mr = 3204.62,Z = 2,Dc = 2.598 g/c^m3,μ = 2.360 mm^-1,F（000） = 3124,the final R = 0.0314,wR = 0.0826 and S = 0.989 for 18592 observed reflections with I 〉 2σ（I）. The crystal packing is stabilized by N–H… and O–H… intraand intermolecular hydrogen bonds to form an infinite 3D network.     

新型化合物[Ni(en)3]2[Ni(en)2(H2O)2][As6V15O42]·4H2O晶体的水热合成与表征

金属氧酸盐因其在医药临床、工业催化、功能材料等方面的广泛应用而引起人们的关注[1～6], 其中, 有关钒化学的研究一直很活跃, 钒具有与钼、钨明显不同的结构特性, 钒可以采取VO4, VO5和VO6方式配位, 同时, 钒的价态可以是+3, +4和+5价. 由于钒可采取多种配位方式及多种价态, 与钼酸盐和钨酸盐相比, 钒酸盐更具有结构柔顺性, 同时易形成低价或混合价态物种.在以往的文献中, 有关P-V-O体系多金属氧酸盐的水热合成的研究已有大量的报道[7], 在常规溶液合成中, 人们已对As-V-O体系进行了相对深入的研究, 而有关水热合成的研究报道却很少, 已见报道的砷钒化合物有K6*6H2O[8,9], 4-[10], 6-[11](X=SO2-3, SO2-4, H2O). 为了探究水热条件下As-V-O体系的反应特性, 我们开展了这方面的研究工作, 并取得了突破性进展. 本文采用中温水热技术合成了含有机基团的砷矾超分子化合物2**4H2O, 探讨这类化合物的非线性光学性质、催化性质及其它功能特性将是一个非常有意义的研究领域.     

C4H8N2H4·Zn(HPO3)2的水热合成和结构表征

在过去的十几年中 ,人们对含有机模板的、由 Zn O4 四面体和 PO4 四面体基本结构单元组成的磷酸锌盐进行了深入广泛的研究 ,发现其结构具有多样性 [1] .近年来 ,人们又开始探索用亚磷酸氢根( HPO3)替代磷酸根 ( PO4 ) ,形成结构新颖的含有机模板的亚磷酸盐 .与磷酸根相比 ,亚磷酸氢根只能与 3个邻近的阳离子通过 P— O— M( M=Zn等 )键相连 ,结构同 [PO3( OH) ]相似 .鉴于此 ,HPO3完全可以作为搭建空旷骨架化合物的结构基元 .与磷酸盐的研究相比 ,以有机胺为模板的过渡金属亚磷酸盐合成研究相对较少 .Harrison等 [2 ,3] 报道了通过…     

一个新型层状化合物[Ni(C10H8N2)2V3O8.5]的水热合成与晶体结构

多金属氧酸盐因其在医药临床、工业催化和功能材料等方面的广泛应用而引起人们的关注[1～7]. 由于钒化合物具有令人感兴趣的结构以及在材料领域中的重要的应用而倍受关注. 在以往的合成中, 常压溶液合成是主要手段, 利用水热合成方法制备多金属氧酸盐配合物晶体是近几年来国际上刚刚兴起的一项研究工作, 通过该方法已合成出一批具有新颖结构的层状、链状、多孔、高聚合度化合物[8～11], 一些已用于药物和催化剂的研究工作中. V-O体系化合物的合成与表征近来已引起人们的极大兴趣, 如: [VⅣVⅤ2O7(phen)]n[12]是一含有混合价钒的层状结构; Ni(en)3(VO3)2[13], Cu(dien)V2O6*H2O[14]是一维链状结构. 为了探究水热条件下钒物种的反应特性及生成规律, 制备新的钒配合物晶体, 目前我们正在积极开展这方面的研究并取得了一定成果.     

Syntheses,Crystal Structures and Properties of Three New Complexes [Ni（C9N2O2H7）2（CH3OH）2],[Zn（C9N2O2H7）2（H2O）2] and [Cd（C9N2O2H7）2（CH3OH）2]

Three novel metal-organic complexes with formulas [Ni(C9N2O2H7)2(CH3OH)2](1),[Zn(C9N2O2H7)2(H2O)2](2) and [Cd(C9N2O2H7)2(CH3OH)2](3) were synthesized by the reactions of Ni,Zn and Cd salts with ethyl 2-benzimidazolylacetate under hydrothermal conditions or layering technique,and characterized by single-crystal X-ray diffraction analysis,IR spec-troscopy,solid-state luminescent properties and thermogravimetric(TG) analysis.The crystal data for these three complexes are as follows:for 1,monoclinic,space group P21/c,a = 9.384(3),b = 9.634(3),c = 11.292(3) ,β = 95.787(5)°,V = 1015.7(5) 3,Z = 2,F(000) = 492,Dc = 1.547 Kg/m3,μ = 1.002 mm-1,the final R = 0.0451 and wR = 0.0900 for 1833 observed reflections with Ⅰ 2σ(Ⅰ);for 2,orthorhombic,space group Pbca,a = 10.031(4),b = 10.379(4),c = 17.525(7),V = 1824.6(12) 3,Z = 4,F(000) = 928,Dc = 1.645 Kg/m3,μ = 1.392 mm-1,the final R = 0.0452 and wR = 0.0996 for 1661 observed reflections with Ⅰ 2σ(Ⅰ);for 3,monoclinic,space group P21/c,a = 9.9114(13),b =10.4852(15),c = 10.4120(14) ,β = 108.453(5)°,V = 1026.4(2) 3,Z = 2,F(000) = 532,Dc = 1.705 Kg/m3,μ = 1.110 mm-1,the final R = 0.0322 and wR = 0.0805 for 1822 observed reflections with Ⅰ 2σ(Ⅰ).In the three complexes,the ethyl 2-benzimidazolylacetate shows the same chelating mode,and the adjacent units are interlinked into a two-dimensional layer through hydrogen-bonds(O-H···O,N-H···O).     

(C2H10N2)[H3As3O10]的水热合成与晶体结构

采用中温水热方法合成了新化合物(C2H10N2)[H3As3O10].利用X射线粉末衍射仪、红外光谱仪、热重分析仪及X射线单晶衍射仪表征了产物的结构.结果表明:该化合物属于单斜晶系,P2(1)/n空间群;晶胞参数为a=0.808 3(6)nm,b=1.446 9(9)nm,c=0.892 0(8)nm,β=98.16°,V=1.032 7(14)nm3,Z=4,F(000)=864,R1=0.025 3,wR2=0.093 4.其化学式为C2H13As3N2O10,分子量Mr=449.90.该化合物是由有机胺阳离子支撑的第一个具有一维链状结构的砷酸盐化合物,相邻的砷酸盐链通过AAAA堆积方式形成三维拓扑扩展结构.