[4,4′-bpyH_2]_5H_2[α-P_2W_(18)O_(62)]_2·4H_2O的合成与结构表征

利用水热方法合成了一种基于双Dawson多阴离子和质子化的4,4′-联吡啶阳离子构筑的化合物[4,4′-bpyH2]5H2[α-P2W18O62]2·4H2O,并经IR光谱、元素分析、热重分析和X射线单晶衍射等测试技术进行了表征.标题化合物属于三斜晶系,P墿空间群,晶胞参数:a=1.35373(5),b=2.24256(13),c=2.73282(11)nm,α=79.890(13),β=77.568(8),γ=80.349(11)°,V=7.9029(6)nm3,Z=2,Dc=4.031g/cm3,GOOF=1.049,R1=0.0674,wR2=0.1434.结构分析结果表明,标题化合物分子由5个质子化的4,4′-联吡啶阳离子、2个H+离子、2个饱和Dawson结构多阴离子[P2W18O62]6-和4个结晶水分子组成.     

Solvothermal Synthesis and Structure of the [Co（5-NH2-bdc）（4,4＇-dpdo）（H_2O）]_n Complex （4,4＇-dpdo = 4,4＇-Bipyridrl-N,N＇-dioxide,5-NH_2-bdc = 5-Aminoisophthalic Acid）

The title compound [Co（5-NH2-bdc）（4,4＇-dpdo）（H2O）]n 1 （5-NH2-bdc = 5-aminoiso- phthalic acid,4,4＇-dpdo = 4,4＇-bipyridrl-N,N＇-dioxide） crystallizes in triclinic,space group P1 with a = 4.999（1）,b = 10.072（2）,c = 13.028（3） A,α = 107.72（3）,β = 92.58（3）,γ = 98.11（3）°,V = 615.9（3） A^3,F（000） = 356,Rint = 0.0186,Z = 2,R = 0.0333,wR = 0.0721,S = 1.032 and （Δ/σ）max = 0.001. In the molecule of 1,the Co（II） cation is coordinated by three O-atoms of two 5-NH2-bdc ligands,one N-atom of another 5-NH2-bdc ligand,one O-atom of 4,4＇-dpdo and one terminal O-atom of water molecule. The molecules construct a 2-D network through bridging 5-NH2-bdc and 4,4＇-dpdo ligands,and further form a 3-D network through N–H and O–H hydrogen bonds. The network topology of 1 can be simplified as a rare 2D （3,6）-connected （426381） net.     

Alternate Array of Zigzag（PbO5）n and（PbO6）n Polynuclear Chains in a 2-D Coordination Polymer with Diverse Coordinate Modes of Nitrate（NO3^-）

A novel metal-organic coordination polymer,[Pb2(NO3)3(Hmppdc)(CH3OH)2]n(1,H2mppdc=2,6-dimethyl-4-phenylpyridine-3,5-dicarboxylic acid),was synthesized from the reaction of H2mppdc,Pb(NO3)2 and CH3OH under solvothermal conditions.X-ray single-crystal diffraction reveals that 1 crystallizes in monoclinic,space group P21/n,with a=10.9883(13),b=7.3603(10),c=31.165(3),β=96.918(2),V=2502.2(5)3,Z=4,Mr=934.75,Dc=2.481 Mg/m3,F(000)=1736,the final R=0.0676 and wR=0.1310(I2σ(I)).Compound 1 contains two distinct 1-D polynuclear metal-oxygen chains((PbO5)n and(PbO6)n),which are bridged by ligands to build up 2-D metal-organic layers,and such layers are further connected to form a 3-D supramolecular network.The new compound exhibits strong photoluminescence in the solid state at room temperature.     

A 2D Layered Thiostannate:Synthesis and Crystal Structure of [tmdpH_2]Sn_3S_7

A new thiostannate,[tmdpH2]Sn3S7 1(tmdp = 4,4'-trimethylenedipiperidine),has been synthesized under solvothermal conditions and characterized by elemental analysis,IR spectroscopy,and single-crystal X-ray diffraction analysis.In 1,the Sn3S4 secondary incomplete cubane-like building units are bridged by μ2-S atoms to form Sn12S12 rings which are then joined parallelly to the [001] plane,giving the final 2D(Sn3S72-)n layer of(6,3) network.The layers are stacked along the c axis so that 24-membered ring channels are generated,in which the organic cations are accommodated.The compound crystallizes in monoclinic,space group C2/c,with a=23.052(3),b=13.4039(12),c=18.412(2),β=120.112(4)°,V=4921.3(9)3,C13H28N2S7Sn3,Mr=792.86,Z=8,Dc=2.140 g/cm3,F(000)=3056,μ=3.619 mm-1,the final R=0.0488 and wR=0.1125 for 4607 observed reflections with I2σ(I).     

Synthesisand Crystal Structure of a Cu（II） Complex with Reduced Schiff-base N-（2-Hydroxybenzyl）-D,L-alanine and 4,4＇-Bipyridine

A new complex [Cu2(sala)2(H2O)2(4,4'-bipy)]·H2O (sala = N-(2-hydroxybenzyl)- D,L-alaninate, 4,4'-bipy = 4,4'-bipyridine) has been synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis and single-crystal X-ray diffraction. The complex crystallizes in monoclinic system, space group C2/c with a = 42.44(3), b = 10.416(8), c = 15.487(13), β = 97.455(14)o, C30H36Cu2N4O9, Mr = 723.71, V = 6789(9)3, Dc = 1.416 g/cm3, Z = 8, F(000) = 2992, μ(MoKα) = 1.308 mm-1, R = 0.0493 and wR = 0.1004 for 4878 observed reflections (I > 2σ(I)). Structural analysis shows that each copper(II) atom displays a distorted square-based pyramidal coordination geometry with two oxygen atoms and one nitrogen atom from one N-(2-hydroxybenzyl)-D,L-alaninate, one nitrogen atom from 4,4'-bipyridine ligand and one water molecule. 4,4'-Bipyridine ligand bridges two Cu(II) ions to form a dinuclear compound. The molecular structure is extended into a one-dimensional wavy chain through hydrogen bonds. These 1D chains are further expanded into 2D networks through hydrogen bonds.     

Syntheses,Structures and Fluorescent Properties of Two 1D Chain Organic Amines and Metal Iodine Organic-inorganic Hybrid Compounds

Two bifunctional amines, 4-(2-aminoethyl)morpholine and histamine, were heated with PbI_2 and BiI_3 in concentrated HI aqueous solution to give one-dimensional(1D) organicinorganic hybrid compounds [(C_6H_(16)N_2O)PbI4]n(1) and [(C_(16)H_(20)N_(20))Bi_2I_(10)](2), respectively. In 1, the [PbI6] octahedra formed double chain anions through sharing-corner and-edge, and the protonated(C_6H_(16)N_2O)~(2+) cations were located at the vicinity of the double chains by hydrogen bonds. In 2, the [BiI_6] octahedra firstly formed dimeric [Bi_2I_(10)]~(4-) anion through sharing edge, and subsequently, the protonated histamine cations worked as bridge to link alternately with [Bi_2I_(10)]~(4-) anion by hydrogen bonds to form organic-inorganic hybrid 1D chains. In addition, compound 1 emitted a green light at the excitation wavelength of 400 nm and the maximum emission wavelength is at 503 nm.     

Synthesis and Crystal Structure of [Cd(NBA)(μ_3-OH)(4,4′-bipy)_(1/2)]_n

A new cadmium polymer [Cd(NBA)(μ3-OH)(4,4′-bipy)1/2]n 1 (NBA = m-nitrobenzoic acid and 4,4′-bipy = 4,4-bipyridine) has been synthesized by hydrothermal reaction. Its structure was determined by single-crystal X-ray diffraction method, and characterized by elemental analysis and IR spectrum. The crystal is of monoclinic, space group C2/c, with a = 15.6912(9), b = 25.9394(15), c = 6.7332(4) ′, β = 114.7700(10)°, V = 2488.4(3) 3, C12H9CdN2O5, Mr = 373.61, Z = 8, Dc = 1.995 g/cm3, μ = 1.776 mm-1, F(000) = 1464, R = 0.0411 and wR = 0.1128 for 2130 observed reflections (I > 2σ(I)). X-ray diffraction studies reveal that the compound features a layered structure, in which 4,4′-bipy ligands bridge Z type of double chains [Cd(μ3-OH)]n and NBA ligands locate at the two sides of the layer. The π-π interactions between the benzene rings of NBA ligands of two adjacent layers lead to the 3D framework.     

Cuprophilicity-induced cocrystallization of [Cu2(4,4'-bpy)(CN)2]n sheets and [Cu(SCN)]n chains into a 3-D pseudopolyrotaxane

The cocrystallization of [Cu(SCN)]n chains and [Cu2(4,4'-bpy)(CN)2]n (4,4'-bpy = 4,4'-bipyridine) layers generated a 3-D pseudopolyrotaxane compound, [Cu2(4,4'-bpy)(CN)2].[Cu(SCN)] (1), which can also be viewed as a 3-D network constructed by linkages of 2-D sheets and 1-D chains via unsupported CuI-CuI interactions. The CuI-CuI contact of 2.651(4) A in 1 is the shortest unsupported CuI-CuI distance documented to date, indicating cuprophilic attractions.     

Structure and Two-dimensional Correlation Infrared Spectroscopy Study of a New One-dimensional Chain Compound:(4,4''-Hbpy)3[NaMo8O26] (4,4''-bpy)2(H2O)4 (bpy = Bipydine)

A novel compound, (4,4'-Hbpy)3[NaMo8O26](4,4'-bpy)2(H2O)4 1 (bpy = bipydine),was synthesized by the hydrothermal method. Single-crystal X-ray diffraction shows that compound 1 belongs to the monoclinic system, space group C2/m with a = 19.1921(5), b = 18.6931(6), c = 9.3821 (3) (A), β = 104.8020(11)°, V = 3254.22(17) (A)3, C50H51Mo8N10NaO30, Mr = 2062.52, Z = 2,F(000) = 2016,μ = 1.591 mm- 1 and Dc = 2.105 g/cm3. The final R = 0.0283 and wR = 0.0912 for 3118 observed reflections (I ＞ 2σ(Ⅰ)). Compound 1 contains the β-[Mo8O26]4- anion, sodium ion, 4,4'-bpy and lattice crystalline water molecules. The β-[Mo8O26] units link the sodium ion to form a chain structure. The infinitechains of [Na(Mo8O26)]3- blocks are surrounded by protonized 4,4'-bpy cations,4,4'-bpy and lattice crystalline water molecules. The 2D-IR correlation spectroscopy study indicates that the stretching vibrations of Mo=O occur more preferentially due to the thermal effect. The TGA analysis shows that compound 1 has high thermal stability.     

(C5H7S2)2[Cu3I5]的合成和晶体结构

我们曾经对二硫代乙酰丙酮和多种金属离子的配合反应进行了系统的研究.在成功合成(C_5H_7S_2)_2[CuBr_3]的基础上,最近我们试图用类似方法合成(C_5H_7S_2)[CuI_3].但对产物晶体的X 射线衍射分析结果却表明,所得到的化合物的分子式为(C_5H_7S_2)_2[Cu_3I_5].[Cu_3I_5]~(2-)是以[CuI_3]配位三角形和两个相邻[CuI_4]配位四面体连接的无限链状配合阴离子形式存在.     

A 2-D Copper Coordination Polymer [Cu(4,4''''-bpy)(H_2O)_4](C_4H_2O_4)(H_2O)_4 Integrated by Hydrogen Bonds and VDW Interactions

1 INTRODUCTION A great deal of interest in transition metal com- plex assembly has recently been devoted to the development of rational synthetic routes to novel one-, two- and three-dimensional crystal frameworks, due to their potential applications in…     

Structure and Two-dimensional Correlation Infrared Spectroscopy Study of a New One-dimensional Chain Compound: (4,4’-Hbpy)_3[NaMo_8O_(26)](4,4’- bpy)_2(H_2O)_4 (bpy = Bipydine)

1 INTRODUCTION Owing to their unusual topological properties and economically important applications in many fields, such as catalysis, biology, materials science and mag- netochemistry[1～3], polyoxometalates (POMs) have aroused particular interest for a long time[4～6]. But the investigation in their capability and application are relatively less carried on. Even though some POMs have been put into practice, the mechanism of the function of POMs remains incompletely understood. Thus,…     

A One-dimensional Transition Metal Complex Constructed from 24-Membered Hinge-shaped Macrocycles with Salicylic Acid and 1,3-Bis（4-pyridyl）propane

A new 1-D coordination polymer [Cd（Hsal）2（bpp）2] 1 was hydrothermally synthesi- zed by self-assembly of the corresponding metal oxide and salicylic acid （H2sal） with exo-bidentate flexible dipyridyl ligand 1,3-bis（4-pyridyl）propane （bpp）. X-ray crystal structure analysis reveals that complex 1 crystallizes in monoclinic,space group C2/c with a = 18.942（3）,b = 12.9309（19）,c = 16.504（2） A,β = 120.072（2）°,V = 3498.3（9）A^3,Z = 4,C40H38CdN4O6,Mr = 783.14,Dc = 1.487 g/cm^3,μ = 0.679 mm^-1,F（000） = 1608,R = 0.0619 and wR = 0.1435 for 3153 observed reflections （I 〉 2σ（I））. The most remarkable feature of 1 lies in the 1-D chain by repeating [Cd2（bpp）2] units which consist of a 24-membered macrocyclic ring. The 1-D motifs are further connected by C–H… O hydrogen bonds to generate a 2-D structure. In addition,thermal stability and luminescent property of compound 1 were also documented.     

Two Polymorphs of the Inclusion Compound [（n-C4H9）4N] ＋（C13H9O3）-H2O

Two polymorphs of the inclusion compound [(n-C4H9)4N]+·(C13H9O3)-·H2O havebeen prepared and characterized by X-ray crystallography. Polymorph 1: triclinic P 1 , a =13.4982(2), b = 13.5743(2), c = 17.1996(2) , α = 67.045(1), β = 77.845(1), γ = 88.762(1)°, V =2830.43(7)3, Z = 4, R = 0.0491, wR = 0.1276; Polymorph 2: tetragonal P43, a = b = 13.53690(1) , c = 30.8491(8) , V = 5653.02(16)3, Z = 8, R = 0.0448, wR = 0.0984. In these two crystalstructures, the hydrogen-bonded ribbons built of 4,4 -dihydroxybenzophenone (DHBP, C13H10O3)anions and water molecules are orderly arranged to generate two-dimensional host layers, withtetrabutylammonium cations contained between the layers to form the sandwich-like inclusioncompounds. The structures of 1 and 2, which exist as two polymorphs, both display the similarpacking pattern and hydrogen-bond linking model.     

One-dimensional indium sulfides with transition metal complexes of polyamines

Three new indium sulfides, [Ni(dien)2]0.5[InS2] (dien = diethylenetriamine) (1), [Ni(dap)3]0.5[InS2] (dap = 1,2-diaminopropane) (2), and [Ni(tepa)]2[In4S7(SH)2].H2O (tepa = tetraethylenepentamine) (3), have been prepared under solvothermal conditions and characterized by single-crystal X-ray diffraction. Compounds 1 and 2 consist of discrete 1-D {[InS2]-} infinity chains with complex cations as charge-compensating ions, while compound 3 consists of a novel 1-D anionic chain constructed from arachno-shaped In4S11 clusters. The sulfide chain of 3 coordinates into the complex cations via the nonterminal S atoms of the polymeric anion, forming a covalently linked organic-inorganic hybrid compound.     

Synthesis, Crystal Structure and Photocatalytic Properties of a Supramolecular Assembly Based on Keggin Polyoxotungstate

A new supramolecular compound (4,4'-bipyH)4[SiW12O40](4,4'-bipy) (4,4'-bipy = 4,4'-bipyridine) was synthesized hydrothermally and characterized by single-crystal X-ray diffraction and IR spectrum. The crystallography analysis for the title compound reveals that the crystal crystallizes in monoclinic, space group C2/m with a = 22.2767(12), b = 21.1879(11), c = 15.6942(8) , β = 97.068(3)°, V = 7351.3(7) 3, C50H44N10O40SiW12, Mr = 3659.24, Z = 4, Dc = 3.306 g/cm3, F(000) = 6544, GOOF = 1.137, R = 0.0577 and wR = 0.1579. The title compound consists of a discrete Keggin-type [SiW12O40]4- anion, one 4,4'-bipy and four protonated (4,4'-bipyH)+ cations. The [SiW12O40]4- anion and protonated 4,4'-bipy are connected to form a supramolecular structure by hydrogen bonds. Meanwhile, the title compound exhibits good photocatalytic activity for color degradation of Rhodamine-B dye solution under visible-light irradiation.     

Synthesis, Structure and Fluorescent Pr.operty of a Novel 2-D Sheet Inorganicorganic Hybrid Cadmium Polymer [CdBr2（bpdo）]n

A novel 2-D sheet inorganic-organic hybrid cadmium polymer,[CdBr2(bpdo)]n (bpdo=N,N'-O,O-4,4'-bipyridine) has been hydrothermally synthesized and characterized by elemental analysis,IR and single-crystal X-ray diffraction. The crystal crystallizes in monoclinic,space group C2/c,with a=16.336(3),b=3.9904(5),c=18.479(3),β=91.640(6)°,Mr= 460.40,V=1204.1(3)3,Z=4,Dc=2.540 g/cm3,μ=8.439 mm-1,F(000)=864,R=0.0314 and wR=0.0733 for 1069 observed reflections (I > 2σ(I)). X-ray diffraction reveals that the title compound consists of the 2-D inorganic-organic hybrid sheet constructed from [CdBr2]n chains and bpdo bridges in the packing motif of…ABAB….The title compound exhibits intense blue photoluminescence in the solid state at room temperature.     

Synthesis, Characterization and Crystal Structure of an Inorganic-organic Composite Metatungstate: [Co(4,4''-bipy)2(H2O)4](4,4''-H2bipy)2[H2W12O40]·5.5H2O

A novel hybrid compound [Co(4,4'-bipy)2(H2O)4](4,4'- H2bipy)2[H2W12O40]·5.5H2Ohas been synthesized from an acidified aqueous solution and characterized by elemental and thermal analyses, IR and UV spectroscopy, and single-crystal X-ray structure determination. Structure analysis indicates that the title compound is of monoclinic, space group C2/c, with a = 21.315(9), b = 15.303 (7), c = 24.139(10) (A), β = 105.170(5)o, V = 7599(6) (A)3, Mr = 3706.99, Z = 4, F(000) = 6616, Dc = 3.231, μ = 18.395 mm-1, R = 0.0652 and wR = 0.1594. X-ray crystallographic study shows that the title compound consists of one [Co(4,4'-bipy)2(H2O)4]2 cation, two diprotonated 4,4'-bipyridine molecules, 5.5 water molecules of crystallization, and one metatungstate polyoxoanion [H2W12O40]6-, which approaches an effective Td point symmetry. TG-DTA analysis indicates that the framework of the metatungstate polyoxoanion is collapsed at 587.0 ℃.     

Syntheses and structures of two low-dimensional beryllium phosphate compounds: [C5H14N2]2[Be3(HPO4)5].H2O and [C6H18N2]0.5[Be2(PO4)(HPO4)OH].0.5H2O

The first two low-dimensional beryllium phosphates, [C5H14N2]2[Be3(HPO4)5].H2O (BePO-CJ29) and [C6H18N2]0.5[Be2(PO4)(HPO4)OH].0.5 H2O (BePO-CJ30), have been successfully synthesized under mild hydrothermal/solvothermal conditions. BePO-CJ29 is built up from strict alternation of BeO4 and HPO4 tetrahedra forming a unique one-dimensional double chains with 12-ring apertures. There are pseudo-10-ring apertures enclosed by two double chains through H-bonds. BePO-CJ29 can also be viewed as a pseudo 2-D layered structure stabilized by strong H-bonds. The diprotonated 2-methylpiperazium cations are located at three positions (i.e., inside the 12-ring aperture, inside the pseudo-10-ring aperture, and in the interlayer of the inorganic pseudo-layers. BePO-CJ30 is constructed by the alternation of Be-centered tetrahedra (including BeO4 and HBeO4) and P-centered tetrahedra (including PO4 and HPO4) resulting in a two-dimensional layered structure parallel to the (0 1 1) direction. The complex layer is composed of coupled 4.8 net sheets. The diprotonated 1,6-hexandiamine cations and water molecules reside in the interlayer regions and interact with the inorganic layers through H-bonds. Crystal data are as follows: [C5H14N2]2[Be3(HPO4)5].H2O (BePO-CJ29), triclinic, P1 (No. 2), a = 8.1000(9) A, b = 8.4841(14) A, c = 19.665(2) A, alpha = 89.683(10) degrees, beta = 78.182(8) degrees, gamma = 87.932(9) degrees, V = 1321.9(3) A3, Z = 2, R1 = 0.0523 (I > 2sigma(I)), and wR2 = 0.1643 (all data); [C6H18N2]0.5[Be2(PO4)(HPO4)OH].0.5 H2O (BePO-CJ30), orthorhombic, Pccn (No. 56), a = 26.01(4) A, b = 8.431(12) A, c = 9.598(13) A, V = 2105(5) A3, Z = 8, R1 = 0.0833 (I > 2sigma(I)), and wR2 = 0.2278 (all data).     

Hydrothermal synthesis, crystal structure, conductivity, and thermal decomposition of [Cu(4,4'-bipy)(H2O)(Mo3O10)].H2O

The hydrothermal reaction of (NH(4))(6)Mo(7)O(24).4H(2)O, CuCl(2).2H(2)O, and 4,4'-bipyridine yields bipyridine-ligated copper-trimolybdate monohydrate [Cu(4,4'-bipy)(H(2)O)(Mo(3)O(10))].H(2)O in the monoclinic system with space group of C(2/c) and cell parameters of a = 15.335(2) A, b = 15.535(2) A, c = 15.106(2) A, beta = 101.162(2) degrees, V = 3530.7(9) A(3), and Z = 8. Its structure consists of one-dimensional infinite ([Mo3O10]2-)( infinity ) chains linked through [Cu2(H2O)2(4,4'-bipy)] units. The Mo-O chain contains distorted [MoO(6)] octahedra connected through corner-sharing oxygen atoms into infinite chains along the c direction and each chain is located in the channel formed by four adjacent crossing chains of [Cu(4,4'-bipy)(H2O)](n)(2n+). The crystal shows weak conductivity through Mo-O chain along the c direction and insulating property along either a or b direction. Furthermore, a crystalline bimetallic oxide, CuMo3O10, forms when the title compound undergoes thermal treatment in N(2) atmosphere after the complete removal of the ligands.