An Extended Cu(Ⅱ) Complex Structure Sustained by Hydrogen Bonding and C-H…π Interactions

The title complex [Cu(L1)(L2)(H2O)]·H2O(1,HL1 = N-(imino(pyridin-2-yl)me-thyl)picolinamidine),HL2 = salicylic acid) has been obtained by volatilization method with L1 prepared from 2,4,6-tripyridyl-1,3,5-triazine in situ.1 was fully characterized by single-crystal X-ray diffraction,elemental analysis and FT-IR.This complex exhibits a three-dimensional frame-work constructed through hydrogen bonding and C-H···π stacking interactions.The cyclic voltametric behavior of complex 1 was also investigated.1 belongs to the monoclinic system,space group P21/c with a = 15.112(5),b = 7.115(2),c = 19.899(6) ,β = 112.32°,V = 1979.4(11) 3,Mr = 460.94,Dc = 1.540 g/cm3,F(000) = 948,μ = 1.146 mm-1,Z = 4,the final R = 0.0612 and wR = 0.1813 for 2510 observed reflections with I 2σ(I).     

Syntheses and Crystal Structures of Two Gd（Ⅲ） Hydrogen Supramolecules Based on p-Sulfonatothiacalix[4]arene

Two novel polymeric complexes, [Gd（HsTCAS）（H2O）7]·4H2O 1 and [Gd（HsTCAS） （CH3COCH3）（H2O）6]·6H2O 2 （H4TCAS = p-sulfonatothiacalix[4]arene）, have been synthesized and characterized by single-crystal X-ray diffraction analyses. Complex 1 crystallizes in monoclinic, space group C2/m with a = 20.2308（12）, b = 19.0894（10）, c = 12.2448（7）A, β = 101.847（3）°, V = 4628.1（5）A^3, C24H43GdO27S8, Mr = 1169.25, Z = 4, Dc = 1.690 g/cm^3, F（000） = 2380,μ = 1.879 mm^-1, the final R = 0.0404 and wR = 0.1038 for 5127 observed reflections with I 〉 2σ（I）. Complex 2 is pseudo-isostructural with complex 1.     

杯芳烃超分子对甲醇的识别机理分析及应用

采用四种杯芳烃超分子化合物为吸附涂层物质, 探讨了涂膜石英晶体微天平(QCM)传感方法对环境大气中微量甲醇气体的识别研究, 发现RCT(Resorcinol cyclic tetramer)是对甲醇气体识别最有效的活性涂层材料. 通过RCT-MeOH单晶体的制备并对其进行X-ray衍射结构解析, 发现其识别机制是基于甲醇分子中的甲基与杯芳烃化合物的苯环之间形成了C-H…π键作用. 当RCT涂层质量为28.16 μg时, 涂膜QCM传感器对甲醇的响应最灵敏, 达到0.01245 Hz/ppm. 该传感器对甲醇气体吸附和解吸附的初速度分别为－0.2110 Hz/s和0.09497 Hz/s. 该方法具有响应快、重现性和稳定性好的优点, 对甲醇测定的回收率在97.83%～103.66%之间, 与气相色谱法测定结果一致, 表明该方法可应用于环境大气中甲醇气体含量的检测.     

N-乙氧羰基-N'-取代芳基硫脲晶体中的弱相互作用及超分子结构研究

合成了3种N-乙氧羰基-N'-取代芳基硫脲并确定了其晶体结构, 晶体结构表明, 在这些化合物中存在分子内及分子间的氢键, 分子间的氢键将化合物1和2组装成了一维链状的超分子结构, 由于空间因素, 化合物3没有形成类似于1, 2中的氢键组装成的链状超分子结构, 而是形成了氢键链接的二聚体. 同时在化合物1, 3中还存在分子间的芳环间的π-π相互作用. 在化合物1的晶体中, 这种π-π相互作用使相邻的超分子链之间相互关联. 化合物3的晶体中, 相邻的二聚体间又通过π-π相互作用连接成了无限延伸的一维链状结构.     

类晶加合物(M=Co,Cu, Ni)的晶体结构及分子间相互作用的理论研究

合成了3种化合物 [2-ClPyH]2CoCl4(1), [2-ClPyH]2NiCl4(2)和[2-ClPyH]2CuCl4(3), 单晶X射线衍射法晶体结构测定结果表明, 这3种化合物是同形加合物, 在它们的结构中, [2-ClPyH]+离子呈平面状, 而[MCl4]2-离子为变形的四面体. 晶体结构分析发现晶体中存在N—H…Cl和C—H…Cl氢键, 以及Cl…Cl分子间相互作用和π-π堆积作用. 对自由状态下独立的配位离子进行的几何构型优化, 以及三维周期性条件下几何结构优化的量子化学计算结果表明, 标题化合物中具有方向性和选择性的氢键决定延伸性结构的方向, 而相对较弱的卤素…卤素作用在最终晶体结构的确定中扮演很重要的角色.     

Synthesis,Spectroscopic Properties and Crystal Structure of 3,3＇-（Anthracene-9,10-diyl）bis（1-phenylpropan-1-one）

The compound 3,3'-(anthracene-9,10-diyl)bis(1-phenylpropan-1-one)(C32H26O2,Mr=442.55) has been synthesized by the reaction of 2,2'-(anthracene-9,10-diylbis(methy-lene))bis(1,3-diphenylpropane-1,3-dione) with CsCO3,and its structure was characterized by 1H NMR and single-crystal X-ray diffraction.The crystal of the title compound belongs to monoclinic,space group P21/c with a=9.154(3),b=5.2777(16),c=24.897(7) nm,β=107.337(10)°,Z=2 and V=1.1482 nm3.X-ray analysis indicates that an intermolecular hydrogen bond C(8)-H(8A)…O(1),weak C-H···π between H(9A) and the centre of anthracene rings and weak π-π interactions between two anthracene ring planes are observed.     

Syntheses and Crystal Structures of Two Coordination Compounds CuLCl（H2O） and Ni（L）2 （HL = 2-Carboxy-1,10-phenanthroline）

Two complexes CuLCl（H2O） 1 and Ni（L）2 2 （HL = 2-carboxy-1,10-phenanthroline） have been synthesized and characterized by single-crystal X-ray crystallography. The structure of 1 has a monoclinic space group P21/n with a = 7.985（2）, b = 16.067（3）, c = 9.694（2） A, β = 98.189（30）°, V= 1231.0（4） A^3, Z = 4, Dc = 1.836 g/cm^3,μ =1.998 mm^-1, F（000） = 684, the final R = 0.0301 and wR = 0.0810. The structure of 2 （C26H14N4NiO10） adopts an orthorhombic system, space group Pbea with a = 9.410（2）, b = 23.2410（5）, c = 23.8680（5） A, V = 5219.9（18） A^3, Z = 8, Mr = 601.12, Dc = 1,530 g/cm^3,μ = 0.809 mm^-1, F（000） = 2448, the final R = 0.0448 and wR = 0.1427. The Cu center of complex 1 exhibits a square pyramidal coordination environment with one oxygen and two nitrogen atoms from deprotonated 2-carboxy-1,10-phenanthroline, one oxygen atom from water and one chloride ion. The Ni center of complex 2 assumes a distorted octahedral coordination geometry consisting of two oxygen atoms and four nitrogen atoms of two deprotonated 2-carboxy-1,10-phenanthroline molecules. Supramolecular assembly has been found via noncovalent bonds, such as hydrogen bonds and π-π stacking interactions.     

Syntheses, Crystal Structures and Electrochemical Properties of Two Molybdophosphates

Two molybdophosphate compounds,[Ni(bim)3]2[H2P2Mo5O23]·2H2O 1 and [Zn(bpy)2]2[Zn(bpy)(H2O)]2Zn[Mo6O12(OH)3(HPO4)4]2·9H2O 2 (bim = 2,2'-biimidazole,bpy = 2,2'-dipyridyl),have been synthesized under hydrothermal conditions and structurally characterized by elemental analysis,TG,and IR. The single-crystal X-ray analysis exhibits that 1 consists of one [H2P2Mo5O23]4-,two [Ni(bim)3]2+ cations and two lattice water molecules,while 2 is constructed from one sandwich-type [ZnP4Mo6] anion modified by four Zn-bpy complexes and nine lattice water molecules. The electrochemical behaviors of compounds 1 and 2 have been studied in detail based on solid bulk modified carbon paste electrodes of compound (CPEs).     

Three New d~(10) Coordination Polymers with Arenedisulfonates:Syntheses,Crystal Structures and Luminescent Properties

Three new cadmium or zinc arenedisulfonate complexes [Zn（bpp）2（L）]n 1, { [Cd（bpp）2（1,5-NDS）（H2O）2]·4H2O }n 2 and { [Cd（bpp）2（H2O2）2]·（1,5-NDS） } n 3 （L = 4,4′-bis（2-sulfonatostyryl）biphenyl, bpp = 1,3-di（4-pyd-dyl）propane and 1,5-NDS = 1,5-Naphthalenedisulfonate） have been synthesized from aqueous solution and structurally characterized by infrared spectroscopy, elemental analysis and single-crystal X-ray diffraction. Crystal data for complex 1： space group P21/n, a = 10.559（3）, b = 13.138（4）, c = 17.623（5）A^°, β = 100.852（3）°, V = 2400.9（12） A^°^3 Z = 2, Dc= 1.351 g/cm^3, F（000） = 1016, μ = 0.654 mm^-1, the final R = 0.0412 and wR = 0.0994; Crystal data for complex 2： space group P^-1, a = 8.5642（19）, b = 10.076（3）, c = 12.114（3） A^°, α = 81.623（7）, β = 77.149（8）, γ = 82.787（7）°, V = 1003.6（4） A^°^3 Z = 1, Dc= 1.495 g/cm^3, F（000） = 466,μ = 0.713 mm^3, the final R = 0.0241 and wR = 0.0713; Crystal data for complex 3： space group C2/c, a = 21.6024（15）, b = 9.4608（5）, c = 18.4656（11）A^°, β = 107.359（3）°, V= 3602.0（4）A^°^3 Z = 4, Dc= 1.533 g/cm^3, F（000） = 1704,μ = 0.780 mm^-1, the final R = 0.0229 and wR = 0.0572. The X-ray single diffraction reveals that 1 exhibits a 3D metal-organic framework formed from 2D Zn（bpp）2^2＋ networks connected by L in the third dimension; 2 and 3 possess 3D and 2D architectures constructed from 1D polymeric chains through H-bond. Complexes 1-3 display photoluminescent emissions at 452 and 335 nm, respectively.     

Hydrothermal Syntheses and Crystal Structures of Two Complexes of Cobalt and Manganese Assembled by 4,4'-Oxydibenzoic Acid

Two new coordination polymers [Co(oba)(mbix)]2n·n H2O(1) and [Mn(Hoba)2(H2O)2]n(2)(H2oba = 4,4'-oxydibenzoic acid, mbix = 1,3-bis(imidazol-1-ylmethyl)benzene) have been successfully synthesized under hydrothermal conditions. Their structures have been determined by elemental analyses, IR spectroscopy, UV and single-crystal X-ray diffraction analysis. The intermolecular hydrogen bonding and π-π stacking interactions extend the complexes into a 3D supramolecular structure.     

Syntheses, Crystal Structures and Properties of Two Lanthanide Selenite-carboxylate Compounds

Two lanthanide selenite-carboxylate （LSC） compounds, namely, [Ln8（SeO3）4（2,6- pdc）8（H2O）10]·2H2O （Ln = Pr 1, Sm 2; 2,6-pdcH2 = pyridine-2,6-dicarboxylic acid） have been hydrothermally synthesized and structurally characterized. Both compounds possess two-dimensional layer structures constructed by Ln8（SeO3）4（2,6-pdc）8（H2O）10 clusters connected to each other via bridging carboxylate groups. The structures are further extended into three-dimensional architectures through extensive inter-layer H-bonding between coordinated water molecules and carboxylate groups. The luminescent properties and thermal stability of both compounds have been investigated.     

Syntheses,Crystal Structures and Properties of Two New Transition-Metal-Centered Heteropolytungstates

Two one-dimensional transition-metal-centered polyoxotungstates, that is, [Cu(en)₂][Cu(en)₂(H₂O)][Cu(en)(phen)][CuW₁₂O₄₀]·3H₂O (1) (en = ethylenediamine, phen = phenanthroline) and [Cu(en)₂]₂[Cu(en)₂(H₂O)]₂[V_5.8W_7.2O₄₀(VO)₄]·3H₂O (2) have been synthesized hydrothermally and structurally characterized by elemental analyses, IR spectroscopy, electrochemical analysis, thermogravimetric analysis and X-ray single crystal diffraction. Single-crystal structural analysis reveals that both of them represent one-dimensional structures constructed from transition-metal-centered Keggin-type polyanions bridged by secondary metal coordination groups of Cu-ligand. Noticeably, compound 1 exhibits a helical chain-liked structure, and the anion is coordinated by three Cu-ligand units, representing a copper-centered and tri-supported Keggin structure. In compound 2, the polyoxoanion [V_5.8W_7.2O₄₀(VO)₄]⁸⁻ represents a V-centered tetra-capped pseudo-Keggin structure, and is coordinated by four Cu-ligand units. The three-dimensional supramolecular structures of compounds 1 and 2 are constructed through intermolecular hydrogen bonding interactions. The electrochemical and thermalstable properties of 1 and 2 are also studied. The results show the redox properties of polyoxotungstates are retained in title polymers.     

新型一维链状化合物N-(m-二茂铁苯基)甲酰胺的合成及晶体结构(英)

N-(m-ferrocenylphenyl)-formamide has been synthesized by the reaction of m-ferrocenyl-aniline with DMF, and characterized by elements analysis, IR, ¹H NMR, and X-ray structure determination. The crystallized was in the monoclinic, P2₁/c space group, with a=0.140 94(3) nm, b=0.102 87(2) nm, c=0.100 26(2) nm, β=104.85(3)° and final R indices [I>2σ(I)] R₁=0.072 7, wR₂=0.184 5. An infinite one-dimensional chain is formed by intermolecular hydrogen bonding N-H…O. Cyclic voltammetry was studied comparing with the parent compound (m-ferrocenylaniline). CCDC: 243511.     

双齿甜菜碱衍生物大环及双环镉(Ⅱ)配位化合物的合成与晶体结构

利用甜菜碱衍生物1,5-二(4-羧基吡啶基)-N-甲基二乙胺(L)合成了两种镉(Ⅱ)的配位化合物[Cd2Cl4(H2O)2L2].2H2O和[Cd2(SCN)4(μ-H2O)L2]。用X-射线单晶衍射仪测定了配合物的单晶结构,并对它们进行了元素分析、红外光谱、1H NMR、热重等表征。结构分析表明,前者具有三十六元大环框架,而后者为双环结构。由于缺乏分子之间的强烈相互作用,弱相互作用决定了这两种化合物在晶格中的堆积模式:前者由相邻分子间的π-π和C-H…π相互作用而堆积形成二维砖墙的结构;后者由配位的SCN-阴离子通过S…S弱相互作用联接成一维链状结构。     

Syntheses,Crystal Structures and Optoelectronic Properties of Two New Inorganic Thioantimonates

Two new thioantimonates,(NH_4)_2Sb_(10)S_(16) (1) and K_(1.4)(NH_4)_(0.6)Sb_(10)S_(16) (2),have been synthesized by solvothermal method with the yields of 80%and 85%,respectively.Single-crystal X-ray diffraction (SCXRD)study reveals that 1 crystallizes in the monoclinic space group of Pn with a=8.1284(4),b=19.4587(9),c=9.1030(4)?,β=91.736(5)°,V=1439.14(12)?~3,Z=2,D_c=4.077 g·cm~(-3),F(000)=1576,μ=10.389 mm~(-1),R=0.0343 and w R=0.0624 (I2σ(I));2 also crystallizes in the monoclinic space group of Pn with a=8.0989(6),b=19.3730(17),c=9.0411(6)?,β=91.879(6)°,V=1417.79(19)?~3,Z=2,D_c=4.207 g·cm~(-3),F(000)=1598,μ=10.748 mm~(-1),R=0.0323 and w R=0.0664 (I2σ(I)).The anionic frameworks of two compounds both feature two-dimensional (2D)[Sb_(10)S_(16)]_n~(2n-)layers.The stabilities and optoelectronic properties of 1 and 2 have been characterized.In particular,they are stable under acidic or alkaline conditions (pH=0 or 12.5),showing excellent acid-based resistance.     

Syntheses,Crystal Structures and Magnetic Properties of Two Lanthanide Mononuclear Complexes

Two isostructural lanthanide complexes, [Tb(salen)_2]_3·3C_2H_9N_2·4CH_4O(1) and [Er(salen)_2]_3·3C_2H_9N_2·2CH_4O(2), where H2 salen = N,N?-bis(3-methoxysalicylidene)ethylene-1,2-diamine, have been in situ synthesized under solvothermal conditions and characterized by IR, elemental analysis, powder and single-crystal X-ray diffraction analysis, and magnetic analysis. Single-crystal X-ray diffraction indicates that the complexes crystallize in monoclinic C121 space group. Each lanthanide center is coordinated with four oxygen and four nitrogen atoms from two salen2-ligands, forming distorted square antiprism geometry. Both 1 and 2 exhibit obvious slow magnetization relaxation under an applied 2 k Oe magnetic field.     

Syntheses,Crystal Structures and Luminescent Properties of Two Schiff Base Complexes

Two new transition metal complexes based on chiral Schiff base ligand, namely Zn(L_1)_2(1) and Cd(L_2)2(2)(L 1=(R,E)-3-(2-hydroxy-3-methoxybenzylideneamino)propane-1,2-diol, L2=(R,E)-2-((2-hydroxy-1-phenylethylimino)methyl)-6-methoxyphenol), have been synthesized and characterized. Single-crystal X-ray diffractions reveal that both 1 and 2 crystallize in the same monoclinic space group C_2. 1 is four-coordinated, while 2 is six-coordinated. Complexes 1 and 2 show fluorescent emission at 479 and 580 nm, respectively. Moreover, 1 and 2 exhibit selective and sensitive recognition toward Zn~(2+)/Cd~(2+) ions in the methanol solution.