Synthesis,Crystal Structures,and Optical Properties of AM2(OH)(SeO3)2 (A = Na,Rb; M = Mg,Zn)

Sodium magnesium selenite NaMg₂(OH)(SeO₃)₂ and rubidium zinc selenite RbZn₂(OH)(SeO₃)₂ were prepared by hydrothermal reactions. The crystal structures of the title compounds were determined by single‐crystal X‐ray diffraction. NaMg₂(OH)(SeO₃)₂ crystallizes in the orthorhombic space group Pnma (no. 62) with lattice parameters a = 13.1919(10), b = 6.0415(4), c = 8.2182(6) Å, and Z = 4 and RbZn₂(OH)(SeO₃)₂ crystallizes in the triclinic space group P$\bar{1}$ (no. 2) with lattice parameters a = 4.8698(5), b = 7.3446(8), c = 11.7796(12) Å, α = 82.554(3), β = 78.456(2), γ = 71.603(3)°,and Z = 2. The structure of NaMg₂(OH)(SeO₃)₂ is a three‐dimensional framework consisting of edge‐sharing MgO₆ octahedra and trigonal pyramidal SeO₃^2– groups, whereas the structure of RbZn₂(OH)(SeO₃)₂ is a two‐dimensional layers structure consisting of corner‐sharing [Zn₂O₇] dimers linked by trigonal pyramidal SeO₃^2– groups. The compounds were characterized by the solid state UV/Vis/NIR diffuse reflectance, and FT‐IR spectroscopy.     

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].     

Hydrothermal synthesis, structure and thermal property of a 2-dimensional network: sodium sulfate [Ni(H2O)6(NaSO4)2]

The title compound of [Ni(H₂O)₆(NaSO₄)₂] has been synthesized under hydrothermal conditions and characterized by single crystal X-ray diffraction. The compound crystallizes in space group P2₁/c of the monoclinic system in a cell at 293.2 K of a=6.1820(12) Å, b=12.316(3) Å, c=9.0890(18) Å, β=106.03(3)°, and V=665.1(2) Å³. In the title compound, each SO₄ tetrahedron coordinates with three Na(I) ions and each Na(I) connects to three SO₄ tetrahedrons. Such a coordinate model makes up a two-dimensional network having two different kinds of rings and, in the bigger rings, the [Ni(H₂O)₆]²⁺ ions are located. In the solid state, some hydrogen bonds connect the title compound to form three-dimensional networks, stabilizing the crystal structure. Thermogravimetric analysis shows that there are three steps of weight loss from the beginning of 110 °C and the residue may be the mixtures of NiO₂ and Na₂O.     

Darstellung und Kristallstrukturen der ersten Alkalimetall‐hexacarbonatooxotetraberyllate: K6[Be4O(CO3)6] · 7 H2O und K6[Be4O(CO3)6]

Preparation and Crystal Structures of the first Alkalimetall‐hexacarbonato‐oxotetraberyllates: K₆[Be₄O(CO₃)₆] · 7 H₂O and K₆[Be₄O(CO₃)₆] K₆[Be₄O(CO₃)₆] · 7 H₂O has been prepared by dissolving freshly precipitated Be(OH)₂ in an aqueous KHCO₃ solution. After enriching the title compound by extraction with ethanol the heptahydrate crystallizes from the organic phase (triklin, P1¯ (No. 2) with a = 951, 01(11), b = 958, 45(12), c = 1601, 7(2) pm, α = 79, 253(13)°, β = 78, 943(12)°, γ = 65, 119(12)°, V_EZ = 1290, 6(3)·10⁶ pm³, Z = 2). Thermal decomposition forms rhombohedral crystals of the anhydrous compound (trigonal‐rhombohedric, R3¯ (No. 148) with a = 1416, 42(6), c = 1704, 5(1) pm, V_EZ = 2961, 4(3)·10⁶ pm³, Z = 6).     

一种新颖的六帽Keggin型钼钒砷酸盐——(H3O)3[AsMo12O40(VO)6]·6H2O的水热合成和晶体结构

近年来,含有Keggin结构的杂多酸以其优异的结构可修饰性及其在催化、功能材料和医药等方面的潜在应用而引起人们广泛的研究兴趣.在这一领域中,众多过渡金属取代的Keggin型杂多化合物,尤其是含有钒和铝的多金属氧酸盐由于其独特的电磁特性及结构特点而倍受关注.但迄今为止,只有少数带帽Keggin型结构的杂多阴离子被报道.这些Keggin阴离子通常具有低的V/Mo.     

Synthesis and Crystal Structures of Two New Layered Manganese(II) Diphosphonates: Mn2[{(O3PCH2)2NHR}(H2O)F]·H2O

Two manganese phosphonates Mn₂[{(O₃PCH₂)₂NHR}(H₂O)F]·H₂O (R = ?C₆H₁₁ (1) , ?CH₂C₅H₄N (2) ) have been synthesized by hydrothermal reaction and characterized by single–crystal X–ray diffraction as well as with infrared spectroscopy, elemental analysis and thermogravimetric analysis. The two isomorphous compounds feature layered structures in ab plane, in which the tetramers comprised of two MnO₄F₂ and two MnO₅F polyhedra are cross–linked via phosphonate oxygen atoms to form Mn^II phosphonate layers. The organic groups of the ligands are orientated toward the interlayer space.     

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.     

[CH3NH3][NH3(CH2)6NH3]H3[P2Mo2W16O62]·H2O的水热合成与表征

首次合成了[CH3NH3][NH3(CH2)6NH3]H3[P2Mo2W16O62]·H2O,通过元素分析、红外光谱和X射线单晶衍射对合成产物进行了表征,并用TGA-DSC研究了化合物的热稳定性.晶体属单斜晶系,P21/m空间群,a=1.2596(3)nm,b=1.8715(4)nm,c=1.9816(4)nm,α=γ=90°,β=90.16(3)°,V=4.671(2)nm3,Z=2,Mr=4358.66,Dc=3.100g·cm-3,μ=19.978mm-1,F(000)=3792,R=0.0835,Rw=0.2026.结果表明,在晶体结构内形成了0.7364nm×0.8354nm的微孔.     

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…     

Synthesis,Crystal Structure and Characterization of a new Protonated Magnesium Borophosphate: (H3O)Mg(H2O)2[BP2O8]·H2O

A new protonated borophosphate (H₃O)Mg(H₂O)₂[BP₂O₈]·H₂O ( 1 ) was synthesized under mild hydrothermal conditions and characterized by single‐crystal X‐ray diffraction, FTIR spectroscopy and TG‐DTA. The compound crystallizes in the hexagonal system, space group P6(1)22 (No 178), a = 9.4462(7) Å, c = 15.759(2) Å, V = 1217.8(2) Å³, and Z = 6. There exist infinite helical $^1_\infty$ {[BP₂O₈]^3–} ribbons built up from corner‐sharing PO₄ and BO₄ tetrahedra, which are connected by MgO₄(H₂O)₂ leading to an infinite three‐dimensional open‐framework. The H₃O⁺ ions are located at the free thread of the helical ribbons, whereas crystallized water occupy the channels of the helical ribbons. The dehydration of the compound occurs at a higher temperature which is presumably due to the anisotropic hydrogen bonds in the crystal structure. The luminescent properties of the compound were studied.     

[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.     

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.     

New Hexachalcogeno–Hypodiphosphates of the Alkali Metals: Synthesis,Crystal Structure and Vibrational Spectra of the Hexathiodiphosphate(IV) Hydrates K4[P2S6] · 4 H2O,Rb4[P2S6] · 6 H2O,and Cs4[P2S6] · 6 H2O

The new hexathiodiphosphate(IV) hydrates K₄[P₂S₆] · 4 H₂O ( 1 ), Rb₄[P₂S₆] · 6 H₂O ( 2 ), and Cs₄[P₂S₆] · 6 H₂O ( 3 ) were synthesized by soft chemistry reactions from aqueous solutions of Na₄[P₂S₆] · 6 H₂O and the corresponding heavy alkali‐metal hydroxides. Their crystal structures were determined by single crystal X‐ray diffraction. K₄[P₂S₆] · 4 H₂O ( 1 ) crystallizes in the monoclinic space group P 2₁/n with a = 803.7(1), b = 1129.2(1), c = 896.6(1) pm, β = 94.09(1)°, Z = 2. Rb₄[P₂S₆] · 6 H₂O ( 2 ) crystallizes in the monoclinic space group P 2₁/c with a = 909.4(2), b = 1276.6(2), c = 914.9(2) pm, β = 114.34(2)°, Z = 2. Cs₄[P₂S₆] · 6 H₂O ( 3 ) crystallizes in the triclinic space group with a = 742.9(2), b = 929.8(2), c = 936.8(2) pm, α = 95.65(2), β = 112.87(2), γ = 112.77(2)°, Z = 1. The structures are built up by discrete [P₂S₆]^4? anions in staggered conformation, the corresponding alkali‐metal cations and water molecules. O ··· S and O ··· O hydrogen bonds between the [P₂S₆]^4? anions and the water molecules consolidate the structures into a three‐dimensional network. The different water‐content compositions result by the corresponding alkali‐metal coordination polyhedra and by the prefered number of water molecules in their coordination sphere, respectively. The FT‐Raman and FT‐IR/FIR spectra of the title compounds have been recorded and interpreted, especially with respect to the [P₂S₆]^4? group. The thermogravimetric analysis showed that K₄[P₂S₆] · 4 H₂O converted to K₄[P₂S₆] as it was heated at 100 °C.     

过渡金属配合物连接的多金属钒酸盐[Co(o-phen)]V2O6·H2O的水热合成和晶体结构

多金属氧酸盐 ( POMs)由于结构新奇 ,物理性能优异 ,在催化、医药、材料和光化学等领域有应用前景 ,而受到人们广泛关注 [1～ 8] .近年来 ,水热技术和有机指导剂的引入促进了 POMs的有机 -无机杂化材料如 [N( CH3) 4]5V18O4 6 [2 ]和 [V4 O10 ( phen) 2 ][3]等研究的迅速发展 .以上化合物多数仅以有机胺为抗衡离子或直接配位连接到无机骨架上 .而以过渡金属配合物为结构导向剂的合成策略 ,最近才引起人们的重视[9～ 11] .本文以钒酸盐 -过渡金属配合物作为研究体系 ,在水热条件下合成了一种未见文献报道的由新型过渡金属配合物连接的…     

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.     

[Pb6(H2O)2(cit)4]·3H2O和Pb(tar)(H2O)2两种柔性酸和铅的配位聚合物的水热合成与表征

在水热条件下, 合成了2个含柔性配体柠檬酸和酒石酸的二价铅配位聚合物[Pb6(H2O)2(cit)4]·3H2O(1)(H3cit=citric acid)及Pb(tar)(H2O)2(2)(tar=tartaric acid). 用红外光谱、差热-热重、元素分析、粉末X射线衍射及单晶X射线衍射等手段对化合物进行了表征. 化合物1属三斜晶系, P1空间群, a=0.97053(19) nm, b=0.9764(2) nm, c=1.0955(2) nm, α=109.016(3)°, β=98.380(3)°, γ=92.136(3)°, V=0.9671(3) nm3, Z=2, R1=0.0420, wR2=0.1049, GOF=1.064. 在化合物1的不对称结构单元中, 有3个铅离子以及2个柠檬酸阴离子和2个游离的水分子. 铅离子分别以4, 5, 7配位与柠檬酸配合形成了中性的三维骨架结构. 化合物2属于正交晶系, Pbca空间群, a=1.39739(6) nm, b=0.64922(2) nm, c=1.80354(10) nm, V=1.63620(13) nm3, Z=8, R1=0.0283, wR2=0.0649, GOF=1.014. 在化合物2的不对称结构单元中, 有1个铅离子、1个酒石酸分子和1个水分子, 六配位的铅和酒石酸形成了一维外消旋的无限长链, 链与链之间通过氢键连接成一个三维超分子结构. 在化合物1和2中, 两种配体均出现了α羟基和α羧基螯合的配位模式, 铅的6s孤电子对均显示了立体化学活性, 使配位键分布于半球区域.     

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.     

超分子化合物[H3N(CH2)3NH3]•[Pb2(SIP)2]•6H2O的水热合成与表征

在水热条件下, 用NaH2SIP与Pb(Ⅱ)盐, 以1,3-丙二胺(1,3-PDA)作为结构导向剂进行反应, 得到化合物[H3N(CH2)3NH3]•[Pb2(SIP)2]•6H2O(1). 同时采用单晶X射线衍射、X射线粉末衍射、元素分析、红外光谱和荧光光谱对化合物1进行了表征.     

三维稀土配位聚合物[Ce2(H2btc)(btc)(H2O)2]n的水热合成与晶体结构

含有稀土元素的无机一有机配位聚合物因在光、电、磁及催化等方面具有潜在的应用价值而引起人们的关注．芳香多羧基有机配体在合成配位聚合物和多维超分子研究领域中扮演着重要角色．1，2，4，5-均苯四甲酸(H4btc)由于具有独特的配位能力(btc^4-最多可作为八齿配体)和空间特性，     

Hydrothermal Synthesis and Crystal Structure of Inorganic-organic Hybrid Compound [H3NC2H4NH2]VOPO4

An inorganic-organic hybrid compound, [H_3NC_2H_4NH_2]VOPO_4 was synthesized by means of the hydrothermal method. It was crystallized in a monoclinic system, a space group P2_1/c, with the crystal cell parameters: a=0.92285(11) nm, b=0.72994(9) nm, c=0.98495(11) nm, β=101.280(3)°, V=0.65067(13) nm~3, M_r=223.02 g/mol, D_c=2.277 g/cm~3, Z=4, R=0.0315, ωR=0.0865, GOF=1.085. The VO_5N octahedra chains are corner-linked by PO_4 tetrahedra; the VO_5N octahedra are all trans-linked with V—O bonds being alternately short and long. The monoprotonated ethylenediamine was intercalated between the layers with one end coordinating to V and the other end as an H-bond donor interacting with a terminal O atom of PO_4 from a neighboring sheet. The elementary analysis, infrared spectrum characters and thermal stability were also given.