DBBD及其Cu(I)配位聚合物[CuI(DBBD)2]n的合成

In this article we report the synthesis of (R,S)-4,4′-biquinoline-6,6′-dimethyl-3,3′-dicarboxylate (DBBD) (1) and the formation of copper(I) coordination polymer [CuI(DBBD)₂]_n (2) by inducing a bidentate organic ligand (DBBD). The crystal 1 belongs to monoclinic system with space group P2₁, and a=0.881 30(19) nm, b=1.966 0(6) nm, c=1.478 1(4) nm, β=119.429(12)°, V=2.230 5(10) nm³, D_c=1.276 g·cm^-3. The crystal 2 belongs to orthogonal system with space group Fmm2, and a=2.044 41(17) nm, b=1.543 06(13) nm, c=1.652 45(13) nm, V=5.212 9(7) nm³, D_c=1.669 g·cm^-3, Z=8. CCDC: 292931, 1; 292934, 2.     

二维铅配合物[Pb2(C8H4O4)2(C19H12N4O)2]n·3.5nH2O的水热合成、晶体结构与荧光性质研究

In the title compound, [Pb₂(C₈H₄O₄)₂(C₁₉H₁₂N₄O)₂]_n·3.5nH₂O(1), has been synthesized by the hydrothermal assembly of 1,4-benzenedicarboxylate and 4-(1H-1,3,7,8-tetraazacyclopenta[l]-phenanthren-2-yl)phenol(TCPP) with lead acetate. Elemental analysis, X-ray crystal structure analysis, IR spectrum, thermogravimetric analysis and luminescence property were carried out for the structural determination and characterization of the title compound. Compound 1 crystallizes in triclinic, space group P1 with a=1.013 54(10) nm, b=1.104 84(11) nm, c=1.210 05(12) nm, α=76.812 0(10)°, β=74.814 0(10)°, γ=86.030 0(10)°, V=1.273 1(2) nm³, Pb₂C₅₄H₃₉N₈O_13.5, M_r=1 430.31, Z=1, D_c=1.866 g·cm^-3, μ=6.680 mm^-1, F(000)=691, R=0.027 3 and wR=0.068 7 for 4 042 observed reflections (I>2σ(I)). The compound 1 exhibits two-dimensional network structures, which are further stacked through π-π interactions and hydrogen bonds to form three-dimensional supramolecular polymer. Solid-state luminescent spectrum of the compound 1 indicates intense fluorescent emission. CCDC: 748883.     

不对称Fe-Fe双金属化合物[Cp*Fe(dppe)(C≡CFc))[PF6]n(n=0，1)的合成、结构及光谱性质的研究(英)

A biased bimetallic Fe-Fe complex Cp^*Fe(dppe)(C≡CFc) (1) was synthesized from FcC≡CH (Fc=C₅H₄FeC₅H₅) and Cp^*Fe(dppe)Cl (Cp^*=C₅Me₅). Its one-electron oxidation species [Cp^*Fe(dppe)(C≡CFc)][PF₆] (1a) was also prepared and the spectroscopic properties of 1a was studied. The single-crystal X-ray diffraction analysis of 1 shows that ferrocenylacetylene is bonded at the terminal carbon to the iron center in the Cp^*Fe(dppe) part. Crystallographic data for 1: monoclinic, space group C2/c, with a=4.067 65(14) nm, b=1.260 74(4) nm, c=1.649 89(5) nm, β=104.387(10)°, V=8.195 7(5) nm³, Z=8, D_c=1.354 g·cm^-3, F(000)=3512, μ=0.822 mm^-1. The structure was refined to R₁=0.038 4, wR₂=0.100 0. CCDC: 234893.     

超分子钴(Ⅱ)配合物[CoL(H2O)2]n的合成与结构表征

A mononuclear Cobalt(Ⅱ) complex [CoL(H₂O)₂]_n (H₂L: 4,4′,6,6′-Tetrabromo-2,2′-[ethylenedioxybis(nitrilomethylidyne)]diphenol), has been synthesized and structurally characterized by elemental analysis, IR and X-ray diffraction single crystal structure analysis. The crystal of the complex belongs to monoclinic space group P2₁/c with a=2.516 8(3) nm, b=1.023 43(18) nm, c=0.789 17(14) nm, β=91.375(2)°, V=2.032 1(5) nm³, Z=4, D_c=2.317 Mg·m^-3, μ(Mo Kα)=8.747 mm^-1, F(000)=1 356, R₁=0.049 7, wR₂=0.110 4. The crystal structure of [CoL(H₂O)₂]_n indicates that the complex consists of one cobalt(Ⅱ) atom, one L^2- unit and two coordinated water molecules, and the coordination number of the cobalt(Ⅱ) atom is six. One-dimensional chain supramolecular structure is formed by intermolecular hydrogen bonds and π-π stacking of neighboring benzene rings. CCDC: 652649.     

锡(Ⅳ)N,N-二取代荒酸配合物Ph3SnS2CN(CH3)C6H5、 Ph3SnS2CN(C4H8NH)和SnCl2(S2CNEt2)2的合成、表征及晶体结构

Three tin (Ⅳ) complexes with N,N-dialkyl dithiocarbamates Ph₃SnS₂CN(CH₃)C₆H₅ (1),Ph₃SnS₂CN(C₄H₈NH) (2) and Sn(Cl)₂(S₂CNEt₂)₂ (3) have been synthesized. The crystal structures have been determined by X-ray sin- gle crystal diffraction. A crystal of the complex 1 is triclinic with space group P1, a=0.9485(3)nm, b=1.0491(3)nm, c=1.3631(4)nm, α=70.996(4)°, β=72.294(4)°, γ=79.609(4)°, Z=2, V=1.2168(6)nm³, D_c=1.453g·cm^-3, μ=1.234mm^-1, R=0.0442, wR=0.0858. A crystal of the complex 2 is monoclinic with space group P2(1)/c, a=1.2214(2)nm, b=1.1651(2)nm, c=1.5769(3)nm,β=99.039(2)°, Z=2, V=2.2162(7)nm³, D_c=1.532g·cm^-3, μ=1.352mm^-1, R=0.0267, wR=0.0591. A crystal of the complex 3 is triclinic with space group P1, a=0.7179(2)nm, b=0.9256(3)nm, c=1.5327(5)nm,α=93.857(4)°,β=98.992(4)°, γ=109.481(4)°, Z=2, V=0.9405(5)nm³, D_c=1.717g·cm^-3, μ=2.076mm^-1, R=0.0263, wR=0.0662. In the complexes 1 and 2 the tin atoms rendered five-coordination in a distorted tigonal bipyramidal structure and in the complex 3 the tin atom rendered six-coordination in a distorted octahedron structure. CCDC: 1, 179918; 2, 180024; 3, 180004.     

一维链状冠醚配合物:[{Na(18-C-6)}2(H2O)]n[M(SCN)4]n(M=Pd、Pt)的合成与结构

The reactions of 18-crown-6 with Na₂[M(SCN)₄] (M= Pd,Pt) were studied and the complex 1 [{Na(18-C-6)}₂(H₂O)]_n[Pd(SCN)₄]_n and complex 2 [{Na(18-C-6)}₂(H₂O)]_n[Pt(SCN)₄]_n were characterized by ele-mental analysis, IR and X-ray diffraction analysis. The complexes belong to monoclinic, space group P2₁/n with cell dimensions, 1:a=1.05734(7),b=1.42250(10),c=1.47762(10) nm,β=107.5330(10)°,V=2.1192(2)nm³,Z=2,D_calcd=1.460g·cm^-3,F(000)=964,R₁=0.0406,wR₂=0.1264 and 2:a=1.05985(19),b=1.4237(3),c=1.4744(3) nm,β=107. 096(3)°, V=2.1264(7)nm³,Z=2,D_calcd=1.690g·cm^-3,F(000)=1028,R₁=0.0292,wR₂=0.0859. In the solid state, the complexes 1 and 2 show an one-dimensional chain of [{Na(18-C-6)}₂(H₂O)]²⁺ complex cations and [M(SCN)₄]^2- (M=Pd,Pt) complex anions bridged by Na-N in-teractions.     

一种新颖有机-无机杂化配位聚合物[(C10H16N)2（Pb2I6）·2DMF·H2O]n的自组装合成和晶体结构(英)

A novel coordination polymer [(C₁₀H₁₆N)₂（Pb₂I₆）·2DMF·H₂O]_n (C₁₀H₁₆N=N-butyl-2-Methy-Pyridinium) was synthesized by the reaction of Pb(NO₃)₂ with C₆H₁₀NI at room temperature in DMF solvent and structurally characterized by means of X-ray single diffraction. The title compound crystallizes in triclinic system, space group P1 with a=1.1237(2) nm, b=1.25330(16) nm, c=0.808 00(12) nm, α=102.523(4)°, β=92.475(5)°, γ=95.712(10)°, V=1.102 9(3) nm³, Z=1, D_c=2.470 Mg·m^-3, F(000)=738, chemical formula C₂₆H₄₈N₄O₃Pb₂I₆ and M_r=1 640.46, μ（MoKα）=11.849 mm^-1, the final R=0.057 8 and wR=0.166 5 for 3716 observed reflections with I > 2σ(I). The title compound consists of cations ([(C₁₀H₁₆N)⁺] and anion chain(PbI₃^-),they are combined by static attracting forces in the crystal. DMF and H₂O locate between the organic and inorganic moiety. CCDC: 210812.     

配位聚合物[Mn(2，4，6-TMBA)2(H2O)3]n·2nH2O的水热合成和晶体结构

The title compound, [Mn(2,4,6-TMBA)₂(H₂O)₃]_n·2nH₂O(1), where 2,4,6-TMBA=2,4,6-trimethylbenzoic acid, was synthesized and its crystal structure was determined by X-ray diffraction analysis. The crystal is of monoclinic, space group C2/c with a=2.929 9(6) nm, b=1.036 4(2) nm, c=8.222 04(17) nm, V=2.494 7(9) nm³, Z=4, M=471.40, D_c=1.255 g·cm^-3, μ=0.571 mm^-1, F(000)=996, R_int=0.029 4, R=0.037 6 and wR=0.094 9. The Mn atoms are octahedrally coordinated by two O atoms of two ligands and four O atoms of water. The carboxyl group coordinates to Mn(Ⅱ) in the mode of monodentate, while the O atoms of water molecules coordinates in bridging mode. The complex shows a one-dimensional chain structure bridged by water molecules. CCDC: 297750.     

桥联双核配合物[(DPC)2Co2(H2O)5]·2H2O的合成与晶体结构

The new complex formulated [(DPC)₂Co₂(H₂O)₅]·2H₂O (HDPC^- is pyridine-2,6-dicarboxylate) has been synthesized and the crystal structure was determined by X-ray diffraction. The crystal structure of the complex belongs to monoclinic system with space group P2₁/c, a=0.83850(10) nm, b=2.7386(4) nm, c=0.9610(2) nm, β=98.280 (10) °, V=2.1838(6) nm³, Z=4, D_c=1.746 g·cm^-3, μ=1.597 mm^-1. In the crystal the two Co²⁺ are in distorted octahedrons. The part of [Co(DPC)₂] possess an approximate D_2d symmetry, while the part of [OCo₍₂₎(OH₂)₅] has an approximate C₂ symmetry.     

三维异核Mn-Na配合物[MnNa(N3)4(C5H5N)4]的合成与表征

Azide-containing coordination polymers have received considerable attention for the construction of new molecule-based magnets. A three dimensional heteronuclear Mn-Na compound [MnNa(N₃)₄(C₅H₅N)₄] was obtained by reaction of [Mn₃O(O₂CCH₃)₆(py)₃]ClO₄ and NaN₃ in pyridine solvents. The title compound crystallizes in monoclinic space group C2/c, a=1.536 6(2), b=1.045 3(2), c=1.576 3(2) nm, β=90.309(3)°, V=2.531 8(6) nm³, Z=4. In the structure, each Mn³⁺ and Na⁺ ion coordinated with four N atoms from four N₃^- and two N atoms from two pyridine molecules. Each pair of Mn³⁺ and Na⁺ ion are linked by N₃^- bridges into a 3D polymer with PtS topology. CCDC: 706250.     

一种新型多孔道配位聚合物[La(C8H6NO2)3]n的合成及晶体结构表征

A novel porous coordination polymer [La(C₈H₆NO₂)₃]_n was synthesized by hydrothermal reaction of flexible ligands 3-(3-pyridyl)acrylate and La(NO₃)₃·6H₂O. The structure was characterized by elemental analysis， IR spectroscopy and X-ray single crystal diffraction. X-ray single crystal analysis reveals the structure consists of [La(C₈H₆NO₂)₃]_n. It crystallizes in monoclinic crystal system with space group P2(1)/c. Crystallographic date: a=0. 7889(3)nm， b=2.5916(9)nm， c=1.1489(4)nm， α=90.00°， β=95.219(6)°， γ=90.00°， V=2.3393(15)nm³， Z=4， D_c=1.656g·cm^-3， μ=1.871mm^-1， F(000)=1152， R₁=0.0328， wR₂=0.0522. CCDC: 211700.     

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.     

一种二帽pseudo-Keggin结构簇合物[HN(C2H5)3]3[N(C2H5)3]2[MoⅣ8MoⅤ4VⅣ2O38(PO4)]的水热合成、结构和性质研究

The novel polyoxometalate, [HN(C₂H₅)₃]₃[N(C₂H₅)₃]₂[Mo^Ⅳ₈Mo^Ⅴ₄V^Ⅳ₂O₃₈(PO₄)], was synthesized and characterized by elementary analysis, EPR, IR spectra and X-ray diffraction. The compound crystallizes in triclinic system, space group P1 with a= 1.41999(2)nm, b=1.43467(2)nm, c=1.694610(10)nm, α=95.7250(10)°, β=92.2110(10)°, γ=92.6060(10)°, V=3.42829(7)nm³, Z=2, D_c=2.388g·cm^-3, M_r=2465.10g·mol^-1, μ=2.489mm^-1, F(000)=2388, R₁=0.0584, wR₂=0.1461, S=1.164. The het-eropolyanion is a bi-capped pseudo-Keggin complex. CCDC： 186645.     

{(n-Bu4N)2[Mo2O2S6Cu6Br4(4，4′-bipy)3]·0.5H2O}n的合成与晶体结构

Cluster coordination polymer {(n-Bu₄N)₂[Mo₂O₂S₆Cu₆Br₄(4,4′-bipy)₃]·0.5H₂O}_n (4,4′-bipy=4,4′-bipyridine), has been synthesized and characterized by X-ray crystallography. The polymeric anion {[Mo₂O₂S₆Cu₆Br₄(4,4′-bipy)₃]^2-}_n is composed of secondary building units (SBUs) [MoOS₃Cu₃], Br atoms and 4,4′-bipy ligands. Two secondary building units [MoOS₃Cu₃] and a double parallel 4,4′-bipy ligands form an octanuclear rectangular metallamacrocycle with the dimension of 1.13×0.39 nm², which is further connected by single bridging 4,4′-bipy ligands to form a 1D zigzag structure. Crystal data for compound 1: C₆₂H₉₇N₈O_2.50S₆Br₄Cu₆Mo₂, M=2 079.68, Triclinic, P1, a=0.982 40(10) nm, b=1.293 70(10) nm, c=1.737 4(2) nm, α=97.810(10)°, β=101.390(10)°, γ=108.520(10)°, V=2.005 1(4) nm³, Z=2, D_c=1.722 g·cm^-3, F(000)=1 039, μ(Mo Kα)=4.055 mm^-1, the final R=0.040 7, wR₂=0.097 2. CCDC: 236407.     

一维链状配位聚合物[Cd{5-(NO2)sal}2(2,2′-bipy)]n的合成与晶体结构

A coordination polymer of [Cd{5-(NO₂)sal}₂(2,2′-bipy)]_n(5-(NO₂)sal=5-nitrosalicylate, 2,2′-bipy=2,2′-bipyridine) was synthesized by hydrothermal reaction and characterized by elemental analysis, IR and X-ray diffraction single crystal structure analysis. The title complex crystallizes in monoclinic with space group C2/c, a=2.730 8(16) nm, b=1.272 3(5) nm, c=0.674 5(3) nm, β=96.73(2)°, V=2.327(2) nm³, Z=4, R=0.022 2, wR=0.057. The 5-nitrosalicylate anions doubly bridge the Cd(Ⅱ) atoms to form one-dimensional polymeric chain with the repeated eight-membered ring units (Cd-O-C-O)₂. The crystal structure is stabilized by intra- and interchain hydrogen bonds interactions. CCDC: 694568.     

配合物[1-(4′-fluorobenzyl)pyridinium]2[Ni(dto)2](dto2-=dithiooxalate dianion)的合成及晶体结构

The complex [1-(4′-fluorobenzyl)pyridinium]₂[Ni(dto)₂] (dto^2- means dithiooxalate dianion) has been pre-pared by reaction of Na₂[Ni(S₂C₂O₂)₂] and the 1-(4′-fluorobenzyl)pyridinium chloride salt. The crystallographic data for the title complex: triclinic P1, a=8.5698(8)?, b=9.3461(9)?, c=10.5361(10)?, α=67.177(2)°, β=67.398(2)°, γ=79.611(2)°, V=717.59(12)?³, Z=1. The [Ni(dto)₂]^2- anion with the Ni atom lying on an inversion center and exhibits a quasi-planar structure. An extensive hydrogen bond network of C-H…O is clearly observed. The nature and size of cation seems to play an important factor in the type of intermolecular interactions as well as the crystal packing in this kind of complexes.     

有机-无机复合物[H2(PW12O40){Zn(C10H8N2)2(H2O)}]·1.5[Zn(C10H8N2)3]·1.75H2O的合成、结构及性能

An organic-inorganic hybrid complex, [H₂(PW₁₂O₄₀){Zn(C₁₀H₈N₂)₂(H₂O)}]·1.5[Zn(C₁₀H₈N₂)₃]·1.75H₂O has been synthesized hydrothermally and structurally characterized by X-ray crystallography. The crystal belongs to monoclinic, space grounp C2/c, with a=4.709 4(2) nm, b=1.431 77(7) nm, c=2.621 07(1) nm, β=90.125(4)°, V=17.673 4(2) nm³, Z=8, D_c=3.087 Mg·m^-3, F(000)=14 884, μ(Mo Kα)=16.327 mm^-1. The structure was refined to R₁=0.068 7 and wR₂=0.158 0 for 20 128 observed reflections with I>2σ(I). Single crystal structure shows that the title compound is constructed from [PW₁₂O₄₀]^3- cluster anion and [Zn(C₁₀H₈N₂)₂(H₂O)]²⁺ metal-organic complex cation, in which metal Zn(Ⅱ) cation are coordinately bonded to the terminal oxygen of Keggin polyanions. The title compound exhibits good catalytic activity for oxidation of benzaldehyde to benzoic acid. CCDC: 624772.     

含有4,5-二氮芴-9-酮锌(Ⅱ)、钴(Ⅱ)化合物的合成和晶体结构

Two compound crystals of (Hdafo)₂[ZnCl₄]·2H₂O (1) and (Hdafo)₂[CoCl₄]·2H₂O (2) were obtained when we tried synthesizing the mixed ligand compounds of Zinc (Ⅱ) and Cobalt(Ⅱ) with 4,5-diazafluorene-9-one(dafo) and o-phthalic acid, respectively. Their structure was determined by single crystal X-ray diffraction. The crystals all belong to monoclinic system, C2/c space group with crystallographic data:(Hdafo)₂[ZnCl₄]·2H₂O, a=1.6768(5)nm, b=1.2052(3)nm, c=1.3888(4)nm, β=116.793(3), V=2.5053(12)nm³, Z=4, F(000)=1232, M_r=609.57, D_c=1.616g·cm^-3, μ(MoKα)=1.444mm^-1, R₁=0.0373, wR₂=0.0765; (Hdafo)₂[CoCl₄]·2H₂O, a=1.6787(4)nm, b=1.2078(3)nm, c=1.3911(4)nm, β=116.665(3)°, V=2.5204(11)nm³, Z=4, F(000)=1220, M_r=603.13, D_c=1.589g·cm^-3, μ(MoKα)=1.142mm^-1, R₁=0.0257, wR₂=0.0654. The constitutes of the two compounds were proved by elemental, IR Spectra and thermal analyses. CCDC: 1, 198516; 2, 198517.     

一维链状钴配位聚合物{[Co(4，4′-bipy)(C9H8O3N)2](H2O)4}n的溶剂热合成、晶体结构及热稳定性

One novel coordination polymer {[Co(4,4′-bipy)(C₉H₈O₃N)₂](H₂O)₄}_n with p-acetamidobenzoic acid and 4,4′-bipy has been synthesized. It was characterized as crystallizing in the triclinic space group P1, with: a=1.138 1(2) nm, b=1.165 2(2) nm, c=1.223 3(2) nm, α=88.47(3)°, β=88.00(3)°, γ=65.78(3)°, V=1.478 4(4) nm³, D_c=1.446 g·cm^-3, Z=1, F(000)=670. Final GooF=1.106, R₁=0.041 5, wR₂=0.110 4. The crystal structure shows that the cobalt(Ⅱ) ion is lined with one 4,4′-bipy molecule, forming a one-dimension chain with Z-type structure, which coordinated with two nitrogen atoms of two 4,4′-bipy molecules and four oxygen atoms from two p-acetamidobenzoic acid molecules, giving a distorted octahedral coordination geometry. The result of TG analysis shows that the title complex was stable under 230.0 ℃. CCDC: 741932.     

混配配合物[Zn(CF3COO)2(C7H6NS)2]的合成、晶体结构及表征

A mixed complex [Zn(CF₃COO)₂(C₇H₆NS)₂] was synthesized based on the reaction of Zn(CF₃COO)₂ and 2-aminobenzothiazol (C₇H₆NS) in methanol. The structure of the complex was characterized by elemental analysis, IR, ¹H NMR and thermal analysis. The crystal structure of the complex was determined by X-ray single crystal diffraction. The crystal belongs to monoclinic system with space group C2/c, a=3.174 3(9) nm, b=1.010 0(3) nm, c=1.723 1(5) nm, β=118.841(4)°, V=4.839(2) nm³; D_c=1.625 g·cm^-3; Z=8; F(000)=2 368; μ=1.266 mm^-1. CCDC: 600233.