[Cu(HIm)2(PPh3)2](BF4)的合成与晶体结构

A Cu(Ⅰ) complex with mix ligands [Cu(HIm)₂(PPh₃)₂](BF₄) was synthesized and characterized by elemental analysis, IRspectroscopy and X-ray diffraction crystallography. The crystal belongs to monoclinic system and P2₁/c space group, with cell parameters, a=1.2836(3)nm, b=1.5089(3)nm, c=2.0661(4)nm, α=90°, β=101.464(4)°,γ=90°, V=3.9219(13)nm³, Z=4 and D_c=1.374mg·m^-3. The Cu(Ⅰ) is coordinated by two Patoms from triphenylphosphine and two Natoms from imidazole to form the distorted tetrahedral geometry.     

超分子三维氢键网络：{[Cu(phen)3](SO4)(H3PCA)2(8H2O)}的晶体结构

A new complex， {[Cu(phen)₃](SO₄)(H₃PCA)₂(8H₂O)}， was synthesized and structurally characterized by single-crystal X-ray analysis. The complex is composed of copper cations， sulfate anions， 1，10-phenanthroline， protocatechuic acid and lattice water molecules. The structure of H₃PCA， SO₄^2- and waters comprises packing of anionic three-dimensional network by hydrogen bonds with cavities. The complex can be considered as a model of host/guest supramolecule. The three-dimensional hydrogen-bonding network is the host species. The Cu(phen)₃²⁺ cations， guest species， occupied the cavities of the host. And the results demonstrate that the form of protocatechuic acid at pH< 1 should be free ligand. CCDC： 191733.     

L-丙氨酸桥联配位聚合物[Cu2(L-ala)2(phen)2]n·2nClO4·2nH2O的合成及其结构

The complex, [Cu₂(L-ala)₂(phen)₂]_n·2nClO₄·2nH₂O(L-ala=L-alaninate, phen=1,10-phenanthroline) has been synthesized and investigated by elemental analysis, IR spectroscopy, and X-ray diffraction methods. The complex crystallizes in the monoclinic space group P2₁ with a=1.161 1(4) nm, b=0.717 2(2) nm, c=2.074 1(7) nm, β=101.028(6)°, V=1.695 4(9) nm³, D_c=1.760 g·cm^-3, Z=4, μ=1.493 mm^-1, F(000)=916, R=0.052 2, wR=0.127 9 for 7 131 unique reflections. The cations of [Cu₂(L-ala)₂(phen)₂]_n²ⁿ⁺ have an one-dimensional polymeric structure, due to the bridging of two Cu(phen)²⁺ units by a carboxylate group of L-alaninate, and each Cu(Ⅱ) ion is in a slightly distorted square-pyramidal coordination geometry, with the phen (N,N′) and the L-ala(N,O) acting as bidentate ligands in the equatorial plane and another carboxylate oxygen atom from a symmetry-related neighboring L-alaninate ion in the apical position. CCDC: 277541.     

配合物[Mn(bipy)3](ClO4)2的晶体结构和热分析研究

The complex [Mn(bipy)₃]·(ClO₄)₂ was synthesied and characterized by X-ray diffraction. X-ray diffraction result for the single crystal showed that the crystal belongs to triclinic, space group P1, a=0.8123(2),b=1.1024(2), c=1.8646(4)nm,α=102.30(3)°,β=91.00(3)°,γ=99.69(3)°,V=1.6056(6)nm³,Z=2,D_c=1.494g·cm^-3. The thermal decomposition of [Mn(bipy)₃](ClO₄)₂ occurred in a three steps pattern. The reaction mechanism of the first step decomposition was deduced as n(1-α)[-ln(1-α)](n-1)/n with the activation energy of 130kJ·mol^-1.     

[Mn(H2O)(phen)2(PAc)](ClO4)的合成、红外光谱及晶体结构

The complex [Mn(H₂O)(phen)₂(PAc)](ClO₄) was synthesized and investigated by elemental analysis, molar conductivity, IR spectrum and X-ray diffraction methods, where phen=1,10-phenanthroline and PAc=phenylac-etate group. The complex crystallizes in the triclinic space group,P1 , with a=0.9289(2)nm,b=1.2425(2)nm,c=1.4791(3)nm,α=114.34(3)°,β=91.25(3)°,γ=104.65(1)°,V=1.4893(4)nm³,Z=2,F(000)=686,D_c=1.489g·cm^-3,μ=0.589mm^-1. The Mn(Ⅱ) ion has a six-coordinate distorted-octahedral geometry with the four nitrogen atoms of two phen ligands,a coordinated-water oxygen atom, and a carboxylate oxygen atom of PAc^-. There is π-π stacking interaction between two phen rings from two neighbor molecules.     

二维网状配合物[Co(dimb)2(MeOH)2](ClO4)2的合成及晶体结构

设计并合成了一个含咪唑基团的柔性双齿配体:1,3-二(咪唑基-1′-甲基)-5-甲基苯(dimb)(1),并进行了 ¹H NMR和结构表征。通过dimb与高氯酸钴的反应,得到了一个新型的具有二维网状结构的配合物:[Co(dimb)₂(MeOH)₂](ClO₄)₂(2)。X-射线晶体结构测定表明,这两个化合物的晶体学参数分别为:配体(1)属单斜晶系, 空间群     

双核配合物[Cu2(L-Asp)(phen)3(NO3)](NO3)·4H2O的合成及晶体结构

The new complex [Cu₂(L-Asp)(phen)₃(NO₃)](NO₃)·4H₂O (L-Asp=L-aspartic acid and phen=1,10-phenanthroline) has been synthesized and its crystal structure has been determined. The complex crystallizes in the monoclinic with space group P2₁/c, The cell parameters are: a=1.261 3(2) nm, b=1.500 8(4) nm, c=2.230 7(4) nm, β=99.55(1)°, and V=4.164 1(16) nm³，D_c=1.587 g·cm^-3. The complex contains two six-coordinated copper ions, and these two copper ions are connected together by L-aspartate to give rise to a binuclear structure. Hydrogen bonds and π-π stacking interactions are observed in the complex. CCDC: 249250.     

甲酸桥联四核锰配合物[Mn4(O2CH)4(phen)8](ClO4)4·6H2O的水热合成和晶体结构

The title compound, [Mn₄(O₂CH)₄(phen)₈](ClO₄)₄·6H₂O(1), where phen=1,10-phenanthroline, was synthes-ized and its crystal structure was determined by X-ray diffraction structure analysis. The crystal is of monoclinic, space group P2/c with a=1.928 0(16) nm, b=1.297 0(11) nm, c=2.126 4(18) nm, V=5.242 2(8) nm³, Z=2, M_r=2 347.36, D_c=1.487 g·cm^-3, μ=0.659 mm^-1, F(000)=2 400, R_int=0.043 7, R=0.052 3, wR=0.118 6. The Mn atoms are octahed-rally coordinated by two O atoms of two ligands and four N atoms of two 1,10-phenanthroline molecules. The carboxyl group coordinates to Mn(Ⅱ) in the bridging bidentate mode. CCDC: 675520.     

簇合物[(η5-C5Me5)WS3{Cu(PPh3)}3Cl](PF6)的合成及晶体结构

Reaction of a preformed cluster [{(η⁵-C₅Me₅)WS₃}₃Cu₇(MeCN)₉](PF₆)₄ (1) in MeCN with LiCl and PPh₃ gave rise to a tetranuclear cationic cluster [(η⁵-C₅Me₅)WS₃{Cu(PPh₃)}₃Cl](PF₆) (2). The title compound 2 was characterized by elementary analysis, IR, UV-Vis, ¹H NMR, and its crystal structure was determined by X-ray single crystal diffraction. It belongs to monoclinic, space group P2₁/c with a=1.799 8(4) nm, b=2.083 6(4) nm, c=1.913 5(4) nm, β=113.63(3)°, V=6.574(3) nm³, Z=4. The cluster cation [(η⁵-C₅Me₅)WS₃{Cu(PPh₃)}₃Cl]⁺ of 2 contains a strongly distorted, cubane-like structure [WS₃Cu₃Cl] in which one Cl weakly fills into the void of the nido-like [WS₃Cu₃] fragment with three relatively long Cu-Cl distances. CCDC: 270415.     

[{Pt4(en)4(NHCOtBu)4}{Tl(18-crown-6)}2](PF6)6的合成与晶体结构

The compound [{Pt₄(en)₄(NHCO^tBu)₄}{Tl(18-crown-6)}₂](PF₆)₆ has been synthesized by a simple one-pot multicomponent reaction. Its structure was determined by X-ray single crystal diffraction analysis. The cation of the compound consists of one linearly arranged [Pt₄(en)₄(NHCO^tBu)₄]⁴⁺ chain and two [Tl(18-crown-6)]⁺ ions located at the two ends of the platinum chain. The complex crystallizes in a triclinic P1 with a=1.060 5(1), b=1.252 3(1), c=2.015(2) nm, α=107.430(2)°, β=91.032(2)°, γ=101.910(2)°, V=2.489 6(4) nm³, Z=2, R₁=0.074 4, wR₂(I>2σ(I))=0.222 5, S=1.062. CCDC: 294083.     

[Cu(TO)2(H2O)4](PA)2的合成和晶体结构

[Cu(TO)₂(H₂O)₄](PA)₂ was prepared by mixing the aqueous solution of 1,2,4-triazol-5-one(TO) and Cu(PA)₂. The molecular structure and crystal structure of the title complex was determined by X-ray single crystal diffraction method. The crystal is triclinic, space group with a=0.7321(1)nm,b=0.7474(2)nm,c=1.3649(3)nm;α=88.65(2)°,β=85.63(1)°,γ=63.35(1)°;V=0.6655(2)nm³,Z=1. The Cu²⁺ coordinated with two TO molecule through its 2-nitrogen atom and four water molecules and showed an octahedral configuration.     

草酸根桥联的双核铜(Ⅱ)配合物[Cu2(phen)2(H2O)2(μ2-C2O4)](NO3)2的合成及晶体结构

A new binuclear copper(Ⅱ) complex, [Cu₂(phen)₂(H₂O)₂(μ₂-C₂O₄)](NO₃)₂, has been synthesized and characterized by elemental analysis, IR and UV-Vis spectrum. Its crystal structure was determined by single crystal X-ray diffraction techniques. Crystal data: monoclinic, space group P2₁/c, a=0.712 21(8) nm, b=1.170 93(14) nm, c=1.783 7(2) nm, β=111.828(2)°, and V=1.380 8(3) nm³, D_c=1.769 Mg·m^-3, Z=2, F(000)=744, R₁=0.025 4, wR₂=0.069 5, Gof=1.077, Δρ=328～-455 e·nm^-3. The complex is packed by one centrosymmetry binuclear copper(Ⅱ) unit, oxalate dianion and NO₃^- anion. In the molecule structure of the title complex, two Cu(Ⅱ) ions are bridged by oxalate dianion and each Cu(Ⅱ) ions coordinates with two nitrogen atoms from 1,10-phenanthroline ligand and one oxygen atom from water to form a five-coordinate distorted square-pyramidal configuration. The hydrogen bonds are observed between coordinated water molecules and NO₃^- anions. The analysis of the crystal structure indicates that the complex has a two-dimensional stacking network structure, which is formed by intramolecular hydrogen bonds, intermolecular hydrogen bonds and stacking effect of aromatic ring. CCDC: 255345.     

一维梯状配位聚合物{[Cu3(H2O)8(4，4′-bipy)2(smbdc)2]·6H2O}n的合成与晶体结构

In the title complex, {[Cu₃(H₂O)₈(4,4′-bipy)₂(smbdc)₂]·6H₂O}_n, Cu1 and Cu2 have different coordination environment. The 5-sulfo-1,3-benzenedicarboxylic acid (smbdc^3-) ligands form one-dimensional zigzag chains linked by Cu atoms. The two adjacent zigzag chains extend into one-dimensional ladder frameworks bridged by a secondary building unit [Cu(H₂O)4(4,4′-bipy)₂]²⁺. The hydrogen-bond interactions between chains make the complex a three-dimensional open supramolecular network. CCDC: 670975.     

镧与β-丙氨酸配合物{[La2(β-ala)6(H2O)4](ClO4)6·H2O}n的合成及晶体结构

The complex, {[La₂(β-ala)₆(H₂O)₄](ClO₄)₆·H₂O}_n, was synthesized in aqueous solution and its crystal structure was determined by X-ray diffraction method .The crystal is triclinic with space group of .The cell pa-rameters are a=0.946(1)nm, b=1.2917(1)nm, c=2.1726(3)nm,α=76.79(1)°, β=80.85(1)°,γ=83.35(1)°, V=2.5429(5)nm³, Z=2, D_c=1.958g·cm^-3.The complex is an one-dimensional infinite chain. The coordination number of lanthanum ion is nine, forming a distorted tricapped trigonal prism.     

新配合物[Cd(H2O)2(phen)2](PA)2的制备及晶体结构

The new compound was prepared by the reaction of Cd(ClO₄)₂·6H₂O,1,10-phenanthroline (phen)and picric acid (HPA)(ratio 1∶3∶2) in methanol-aqueous solution refluxing for 4 hours. The crystals used for X-ray analysis was obtained by slow evaporation of the solution at room temperature. The crystal compound is in triclinic with space group with a=1.1363(4)nm,b=1.2593(2)nm,c=1.3972(4)nm,α=93.97(2)?,β=100.84(3)?,γ=106.29(2)?,Z=2,V=1.8690(9)nm³,D_c=1.715g·cm^-3, μ(MoKα)=0.677mm^-1,F(000)=972,R=0.0907,wR=0.2240. In the complex, the Cd(Ⅱ) cation is octahedrally coordinated to two 1,10-phenanthroline ligands and two water molecules in cis disposition. As outer sphere, picrate anions are combined with inner by hydrogen bond and static electricity interaction.     

N，N′-双(2-吡啶乙基)二硫代草酰胺根桥联的三核铜(Ⅱ)配合物的合成及性质

Two Trinuclear copper(Ⅱ) complexes bridged with N,N′-Bis(2-pyridylethyl)-Dithiooxamidate, [Cu₃L₂](ClO₄)₂ (1) and [Cu₃L₂](NO₃)₂ (2) (H₂L=N,N′-Bis(2-pyridylethyl)-Dithiooxamide), have been synthesized, and characterized by elemental analyses, IR, UV-Visible spectra, conductance and EPR spectra. The variable temperature magnetic susceptibility for complex 1 has been measured in the temperature range of 1.5～298 K. Experimental data of magnetic susceptibility are successfully fit to theoretical value based on the spin Hamiltonian operator：(?), S₁=S₂=S₃=1/2, giving the magnetic exchange parameters of 2J=-221.6 cm^-1 and 2j=-15.8 cm^-1. This result indicates the presence of a strong antiferromagnetic spin exchange interaction between the Cu(Ⅱ) ions.     

配位聚合物[Mn(4，4′-bpy)1.5(H2O)3](ClO4)·(4，4′-bpy)(L)·H2O的水热合成和晶体结构

The title compound, [Mn(4,4′-bpy)_1.5(H₂O)₃](ClO₄)·(4,4′-bpy)(L)·H₂O(1), where L=2,4,6-trimethylbenzoic acid, was synthesized and its crystal structure was determined by X-ray diffraction analysis. The crystal is of triclinic, space group P1 with a=2.929 9(6) nm, b=1.036 4(2) nm, c=8.222 0(1) nm, α=105.300(2)°, β=97.495(2)°, γ=91.118(2)°, V=1.884 0(4) nm³, Z=2, M_r=780.10, D_c=1.375 g·cm^-3, μ=0.483 mm^-1, F(000)=812, R=0.055 4, wR=0.135 2. The Mn atoms are octahedrally coordinated by three N atoms of three 4,4′-bipyridine ligands and three O atoms of water. The complex shows a one-dimensional chain structure bridged by water and 4,4′-bipyridine molecules. CCDC: 615707.     

二个新颖的一维聚合物{(PyH)3[Cu3Br6]}∞和{(γ-MePyH)2[Cu2Br4]}∞的合成和晶体结构

Reactions of CuBr with equimolar PyHBr or γ-MePyHBr afforded two novel one-dimensional bromocuprate(Ⅰ)polymers {(PyH)₃[Cu₃Br₆]}_∞ (1) and {(γ-MePyH)₂[Cu₂Br₄]}_∞(2)， respectively. Both 1 and 2 were charac-terized by IR， elemental analysis， and X-ray crystallography. Crystal data for 1: monoclinic， space group P2₁/n， a=0.93262(12)nm， b=1.3497(2)nm， c=1.9149(2)nm， β=93.465(7)°， V=2.4060(5)nm³， Z=4. Crystal data for 2: orthorhombic， space group Pbcm， a=0.8659(4)nm， b=1.5669(6)nm， c=1.2849(5)nm， V=1.7432(2)nm³， Z=4. The structure of 1 has a unique helical chain composed of [Cu₃Br₅] units and μ-bromide anions while that of 2 shows a linear chain consisted of [Cu₂(μ-Br)₂] units bridged by pairs of μ-Br atoms. CCDC: 1， 208412; 2， 208413.     

配位聚合物{[CoL][FeⅡFeⅢ(ox)3·1.5H2O]}∞的合成、波谱表征和磁学性质

A new Schiff base complex， CoL(ClO₄)·3H₂O (1) {L represents condensed from equal molar ratio of sali-cylaldehyde and diethylenetriamine} was synthesized and characterized. Further， a new coordination polymer， {[CoL][Fe^ⅡFe^Ⅲ(ox)₃·1.5H₂O]}_∞ (2)， was synthesized and characterized， where ox^2-=oxalate. The results of the IR and M?ssbauer spectra of 2 revealed that the coordination polymer exists 2-D layer structure in the solid state， and anions layer was formed by [^ⅡFe^Ⅲ(ox)₃]^- unit. The magnetic properties of 2 have been measured and the results indicate that there is magnetic ordering in the low temperature， which may arise from intermolecular ferromagnetic interactions or spin canted effects.     

Cu2(μ-dppb)2(μ-Cl)2的合成、晶体结构及非线性光学性质

The complex Cu₂(μ-dppb)₂(μ-Cl)₂ has been synthesized from the reaction of CuCl， dppb and (n-Bu)₄NCl. The crystal belongs to the triclinic with space group P1. The unit cell parameters are: a=9.939(4)?， b=10.083(6)?， c=14.104(5)?， α=76.46(3)°， β=71.02(2)°， γ=70.87(5)°. The single crystal X-ray diffraction analysis reveals that it has a bi-ring structure with a symmetry center at the middle of two Copper atoms. The outer ring is a 14-membered ring of Cu-dppb-Cu-dppb， and the inner ring is a 4-membered ring composed of two Cl^- and two Cu(Ⅰ). Investigation of third-order optical nonlinearity shows that it exhibits considerable nonlinear absorptive and self-defocusing effect with α₂=1.75×10^-13m·W^-1 and n₂=3.19×10^-18m²·W^-1. CCDC: 193113.