Synthesis,Structure and Property of a Novel Coordination Polymer [Tb(C_7H_3NO_4)(C_6H_4NO_2)(H_2O)]

A novel terbium(III) coordination polymer [Tb(C7H3NO4)(C6H4NO2)(H2O)] was successfully synthesized hydrothermally and characterized by single-crystal X-ray diffraction. The complex is of monoclinic, space group P21/c with a = 9.2252(11), b = 14.1477(16), c = 10.5134(12) A, β = 95.770(2)°, V = 1365.2(3) A3, Z = 4, Dc = 2.248 g·cm-3, F(000) = 880, the final R = 0.0176 and w R = 0.0411 for 2149 observed reflections with I 2σ(I). The complex is extended into a three-dimensional network structure with 24-atom rings which are composed of Tb, C and O atoms. The complex displays green fluorescence emission in the solid state at room temperature, which corresponds to 5D4 → 7F5 transition of the Tb(III) ion.     

Synthesis, Crystal Structure and Thermal Stability of a Saturated Dimeric Ce(Ⅲ)-chelated Complex Based on Benzoate and 1,10-Phenanthroline Ligands

The title complex, [Ce(BA)3phen]2 (BA = benzoate, phen = 1,10-phenanthroline),was prepared by the reaction of Ce(NO3)3·6H2O, benzoic acid and 1,10-phenanthroline. The complex was characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra and TG-DTG techniques. The results show that the crystal is of triclinic, space group P(1) with a =10.912(2), b = 11.962(3), c = 12.474(3)(A), a = 104.889(3), β = 93.523(3), γ = 113.332(3)°,C66H46Ce2N4O12, Mr = 1366.90, V= 1420.2(6) (A)3, Z = 1, Dc = 1.598 g/cm3,μ = 1.652 mm-1, S =1.024 and F(000) = 682. The final R = 0.0391 and wR = 0.0947 for 4878 observed reflections with I ＞ 2σ(1). The structure of the title complex consists of two Ce(C6H5COO)3(C12H8N2) units,forming a binuclear molecule. Each Ce(Ⅲ) is coordinated by two O atoms of one bidentate chelating carboxylate group, five O atoms of two bidentate bridging and two tridentate chelating-bridging carboxylate groups, and two N atoms of one 1,10-phenanthroline molecule to complete a distorted monocapped square antiprism geometry. Its thermogravimetric analysis was determined by TG-DTG techniques.     

Synthesis,Crystal Structure and Electrochemical Property of a Dinuclear Manganese（Ⅱ） Complex [Mn_2（C_（12）H_8N_2）_4（C_8H_5O_4）_2]（C_8H_4O_4）·H_2O

One dinuclear manganese(II)complex [Mn2(C12H8N2)4(C8H5O4)2](C8H4O4)·H2O has been synthesized with o-phthalic acid and 1,10-phenanthroline.The crystal structure was determined by X-ray diffraction.The crystal belongs to the triclinic system,space group P1 with a = 1.17767(3),b = 1.22292(2),c = 1.35860(3)nm,α = 110.5300(10),β = 97.6140(10),γ = 93.7300(10)o,V = 1.80307(7)nm3,Dc = 1.404 g/cm3,Z = 2,F(000)= 784,the final GOOF = 1.047,R = 0.0398 and wR = 0.1038.The crystal structure of the title complex consists of one [Mn2(C12H8N2)4(C8H5O4)2]2+ cation,one uncoordinate o-phthalate anion(C8H4O4)2-and one uncoordinate water molecule.In [Mn2(C12H8N2)4(C8H5O4)2]2+,the central Mn(II)ion is coordinated by four nitrogen atoms and two oxygen atoms to give a distorted octahedral coordination geometry.The electrochemical property of the title complex was also studied.     

Synthesis, Crystal Structure and Thermal Stability of a Saturated Dimeric Ce(III)-chelated Complex Based on Benzoate and 1,10-Phenanthroline Ligands

The title complex, [Ce(BA)3phen]2 (BA = benzoate, phen = 1,10-phenanthroline), was prepared by the reaction of Ce(NO3)3·6H2O, benzoic acid and 1,10-phenanthroline. The complex was characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra and TG-DTG techniques. The results show that the crystal is of triclinic, space group P1 with a = 10.912(2), b = 11.962(3), c = 12.474(3) , α = 104.889(3), β = 93.523(3), γ = 113.332(3)o, C66H46Ce2N4O12, Mr = 1366.90, V = 1420.2(6) 3, Z = 1, Dc = 1.598 g/cm3, μ = 1.652 mm-1, S = 1.024 and F(000) = 682. The final R = 0.0391 and wR = 0.0947 for 4878 observed reflections with I > 2σ(I). The structure of the title complex consists of two Ce(C6H5COO)3(C12H8N2) units, forming a binuclear molecule. Each Ce(III) is coordinated by two O atoms of one bidentate chelating carboxylate group, five O atoms of two bidentate bridging and two tridentate chelating-bridging carboxylate groups, and two N atoms of one 1,10-phenanthroline molecule to complete a distorted monocapped square antiprism geometry. Its thermogravimetric analysis was determined by TG-DTG techniques.     

Synthesis, Crystal Structure and Thermal Stability of a Saturated Dimeric Ce（III）-chelated Complex Based on Benzoate and 1,10-Phenanthroline Ligands

The title complex, [Ce（BA）3phen]2 （BA = benzoate, phen = 1,10-phenanthroline）, was prepared by the reaction of Ce（NO3）3.6H2O, benzoic acid and 1,10-phenanthroline. The complex was characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra and TG-DTG techniques. The results show that the crystal is of triclinic, space group P1 with a = 10.912（2）, b = 11.962（3）, c = 12.474（3） A, α = 104.889（3）, β = 93.523（3）, γ = 113.332（3）^o, C66H46Ce2N4O12, Mr = 1366.90, V= 1420.2（6） ,A^3, Z = 1, Dc = 1.598 g/cm^3, μ = 1.652 mm^-1, S = 1.024 and F（000） = 682. The final R = 0.0391 and wR = 0.0947 for 4878 observed reflections with I 〉 2σ（I）. The structure of the title complex consists of two Ce（C6HsCOO）3（C12H8N2） units, forming a binuclear molecule. Each Ce（Ⅲ） is coordinated by two O atoms of one bidentate chelating carboxylate group, five O atoms of two bidentate bridging and two tridentate chelating-bridging carboxylate groups, and two N atoms of one 1,10-phenanthroline molecule to complete a distorted monocapped square antiprism geometry. Its thermogravimetric analysis was determined by TG-DTG techniques.     

Synthesis and Structure of a Novel Chain-like Inorganic-organic Hybrid Constructed from Isopolyanion and Oxalato-bridged Dinuclear Copper Complex

A novel inorganic-organic hybrid based on isopolyanion,{[Cu2(phen)2(μ-ox)][H2Mo8O26]}·4EtOH·Et2O(1) (phen=phenanthroline,ox=oxalate),was synthesized under open-air mild reaction conditions,and characterized by elemental analysis,IR,ICP,TG and single crystal X-ray diffraction analysis.The crystal structure belongs to triclinic system with space group Pī and cell parameters:a=1.1075(5) nm,b=1.1608(5) nm,c=1.3333(5) nm,α=91.683(5)o,β=113.996(5)o,γ=112.170(5)o,V=1.4159(10) nm3,Mr=2017.44,Z=1,Dc=2.366 g/cm3 and F(000)=980.0.The structure of hybrid 1 is a 1D chain constructed of alternating octamolybdate isopolyanions [β-(Mo8O26)4-] and oxalato-bridged dinuclear copper complex cations [Cu2(phen)2(μ-ox)]2+.Ultimately,a 3D supramolecular network was formed by hydrogen bond interactions among the adjacent chains.The result shows that hybrid 1 is the first example of inorganic-organic hybrid constructed from isopolyanion and oxalato-bridged dinuclear copper complex fragment (CCDC No.665101).     

Synthesis and Crystal Structure of a New Lanthanum(Ⅲ) 4-Cyanobenzoate Complex

A new dinuclear La(Ⅲ) complex [La2(4-cba)4[H(4-cba)2]2(phen)2(H2O)4] (4-Hcba = 4-cyanobenzoic acid and phen = 1,10-phenanthroline) 1 has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single- crystal X-ray diffraction. Crystallographic data: C88H58La2N12O20, Mr = 1881.28, triclinic P(1), a = 7.518(3), b = 17.033(6), c = 17.551(6)(A), α = 115.333(4), β = 92.9910(10), γ = 99.366(5)°, V = 1985.3(12) (A)3, Z = 1, Dc = 1.574 g/cm3, F(000) = 944 μ = 1.145 mm-1, the final R = 0.0281 and wR = 0.0686 for 6708 reflections with Ⅰ ＞2σ(Ⅰ). In 1, two nine-coordinated La(Ⅲ) ions are connected by two 4-cba ligands in a syn-syn bidentate coordination mode, and the other six 4-cba ligands terminate the La(Ⅲ) ions, resulting in an isolated dinuclear structure. Two different types of intramolecular hydrogen bonds, asymmetrical O-H…O and symmetrical O…H…O, exist in the crystal. The title complex molecules are connected through hydrogen bonds and weak π-πstacking interactions to generate a 2-D layered network. The thermogravimetric analysis of 1 has also been discussed.     

Synthesis,Characterization and Antitumor Activity in Vitro of Cd（Ⅲ）Complex with Chelidamic Acid

A novel complex [Cd4(HCAM)4(H2O)8] of Cd(Ⅲ) withchelidamic acid (H3CAM) was synthesized by the hydrothermal method and characterized with IR and emission spectra.The crystal structure was determined based on single-crystal X-ray diffraction data.It crystallizes in monoclinic,space group C2/c with a=17.538(5),b=12.916(4),c=16.505(7),β=100.690(14)o,V=3674(2) 3,Z=8,C14 H14 Cd2N2O14,Mr=659.07,Dc=2.383 g/cm 3,μ=2.400 mm-1,S=1.000,F(000)=2560,the final R=0.0242 and wR=0.0581 for 3656 observed reflections with I>2σ(I).The inhibition of the complex against K562 and HL60 cells was determined by MTT assay.The results showed that the concentration of complex was positively correlated with inhibitions against K562 and HL60 cell lines,but inhibitory effects are relatively weak.IC 50 concentration of the title complex on K562 and HL60 cells is 15 and 5 μg/mL,respectively.     

杂-双核配合物[CaCu(C3H2O4)2(H2O)4]n的合成、晶体结构及热稳定性

The title complex, [CaCu(C3H2O4)2(H2O)4]n, with a formula of C6H12CaCuO12 and Mr=379.78 has been sy-nthesized and characterized by single crystal X-ray diffraction structure analysis, elemental analysis, IR spectra and TG-DTG techniques. The results show that the crystal is Orthorhombic, space group Pbcn with a=0.669 21(5) nm, b=1.370 23(5) nm, c=1.322 39(10) nm, V=1.212 59(16) nm3, Dc=2.080 g·cm-3, μ=2.288 mm-1, F(000)=772 and Z=4. The final R=0.054 0 and wR=0.112 8 for 1 189 observed reflections with I>2σ(I). The structure of the title complex consists of CaO8 polyhedra and CuO6 elongated octahedra linked together by malonate ligands. The Ca(Ⅱ) cation, on a twofold axis, is coordinated by two water molecules and six malonate O atoms. The Cu(Ⅱ) cation, which lies in a centre of symmetry in an octahedral arrangement, is coordinated by four malonate O atoms and two water molecules. The structure comprises alternating layers along the [101] plane, with the shortest Cu…Cu distance of 0.762 46(6) nm. The whole 3D structure is maintained and stabilized by the presence of hydrogen bonds. Its thermo gravimetric analysis was determined by TG-DTG techniques. CCDC:663184.     

Synthesis and Structural Characterization of Bis(2,2'-bpy)bis(azide)cobalt(III) nitrate dihydrate

The title complex [CoIII(2, 2?-bpy)2(N3)2]@NO3@2H2O was obtained by an auto-oxidization reaction of cobalt nitrate with 2, 2?-bpy and sodium azide in aqueous solution at room temperature, and violet single crystals were prepared in ethanol solution. The structure was determined by X-ray crystallography. The crystal is of triclinic, space group P ī with a = 8.285(4), b = 11.990(8), c = 12.596(7) ?, ( = 86.630(3), ( = 86.280(5), ( = 71.130(10)°, C20H20CoN11O5, Mr = 553.40, Z = 2, V = 1180.6(12) ?3, F(000) = 568, Dc = 1.557 g/cm3, ( = 0.784 mm-1, R = 0.0403 and wR = 0.1008. The title complex consists of a [CoⅢ(2, 2?-bpy)2(N3)2]+ cation, a NO3- anion and two lattice water molecules. The center CoⅢ ion coordinated by two chelating 2, 2?-bpy ligands and two terminal azide groups with a CoN6 coordination environment exhibits a distorted octahedral geometry.     

Synthesis and Structure Characterization of a Manganese(Ⅱ) Complex With Eight Coordination Geometry: [Mn(O_2CMe)_2(phen)_2]

The title compound [Mn(O2CMe)2(phen)2] (phen = 1,10-phenanthroline) 1 has been synthesized and structurally determined by single-crystal X-ray diffraction. The crystal is of orthor- hombic, space group Pbcn, with a = 12.554(4), b = 10.168(3), c = 17.704(5) , V = 2259.7(12) 3, Z = 4, C28H22MnN4O4, Mr = 533.44, Dc = 1.568 g/cm3, F(000) = 1100, Rint = 0.0242, T = 293(2) K and μ = 0.631 mm–1. The final R = 0.0687 and wR = 0.1960 for 2046 observed reflections with I > 2σ(I). The structure of the complex consists of one Mn(II) core coordinated by two bidentate-bound CH3COO- groups and two η2-phen groups forming an eight-coordinate geometrical configuration.     

Synthesis and Crystal Structure of a Two—dimensional Polymeric Holmium

The title polymeric complex [Ho(H2saln)1.5(NO3)3](H2saln=N,N'-bissalicyclidene-ethylenediamine) C24H24N6O12Ho was prepared and its crystal was characterized by X-ray diffraction. The ligand is dischiff base from salicylaldehyde and ethylenediamine. The complex crystallizes in trigonal system, space group Pc1(No. 165), Mr=753.42, a=15.818(2), c=16.978(3) , V=3681(2) 3, Dx=1.360 g/cm3, Z=4, μ=2.2286 mm-1, F(000)=1492, R=0.049, Rw=0.061. In the complex the coordination number of Ho(Ⅲ) is 9 with the geometry of a tricapped trigonal prism. All of the coordination atoms are oxygen atoms. The Ho(Ⅲ) ions are bridged by the dischiff base to form an infinite two-dimensional polymeric network, parellel to the (001) plane.     

Syntheses and Crystal Structures of a Series of Coordination Complexes Derived from the Fluorescein Ligand

Solvothermal reaction of lanthanide(Ⅲ) salts with fluorescein (2-(6-hydroxy3-oxo-3H-xanthen-9-yl)benzoic acid) led to a series of new coordination polymers {[Ln(C 20 H 11 O 5)(C 20 H 10 O 5)(H 2 O)]·DMF} n (Ln=Er,Eu,Gd,Tb,Tm,Yb).The PXRD patterns of the complexes indicate they are isomorphous.The structure of complex {[Er(C 20 H 11 O 5)(C 20 H 10 O 5)(H 2 O)]·DMF} n has been determined by single-crystal X-ray diffraction,revealing a 2D framework in which DMF molecules were filled between the layers.The crystal structure belongs to the triclinic system,space group P1,with a=12.107(4),b=12.232(4),c=13.273(4),α=68.005(7),β=88.024(11),γ=77.451(8)°,V=1776.7(9) 3,Z=2,D c=1.720 g/cm 3,μ=2.434 mm-1,F(000)=918,R int=0.0584,T=293(2) K,the final R=0.0621 and wR=0.1501.     

Synthesis, Crystal Structure and DNA Binding Studies of a Nickel（II） Complex with 2-Aminomethylbenzimidazole and Demethylcantharate

A new mixed-ligand nickel(Ⅱ) complex, [Ni(L)(DCA)(H2O)]·2H2O (L = C8H9N3, 2-aminomethyl-benzimidazole, DCA2- = 7-oxabicyclo[2,2,1]heptane-2,3-dicarboxylate, demethylcantharate, C8H8O5), has been synthesized and characterized. The structure of the complex was determined by single-crystal X-ray diffraction. It is of monoclinic system, space group P21/c with a = 7.7211(7), b = 12.0799(12), c = 19.7867(19), β = 100.390(6)°, V = 1815.2(3) nm3, Dc = 1.625 g·cm-3, Ζ = 4, F(000) = 928, R = 0.0314 and wR = 0.0822. In addition, the interaction between the complex and DNA was studied by means of fluorescence spectra and viscosity. The results indicate that the complex binds to DNA by the mode of partial intercalation with the Stern-Volmer constants Ksv of 3.81 × 104 mol·L-1.     

Supramolecular Terbium-SIP Complex Pillared by 4,4'-Bipyridyl,{[Tb(SIP)(H_2O)_5]_2(bpy)_3(H_2O)}n:Synthesis,Crystal Structure and Photoluminescence

The supramolecular terbium complex, {[Tb(SIP)(H2O)5]2(bpy)3(H2O)}n (NaH2SIP= 5-sulfoisophthalic acid monosodium salt and bpy=4,4'-bipyridyl), has been synthesized by the hydrothermal reaction of Tb4O7 with NaH2SIP and bpy at 165 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, powder X-ray diffraction and photoluminescence spectrum. It crystallizes in a monoclinic system, space group C2/c, with a= 30.6840(1), b=10.9206(2), c=17.4967(3), β=111.931(1)o, V=5438.65(14)3, Z=4, C46H52N6O25S2Tb2, Mr=1470.90, Dc=1.796 g/cm3, μ=2.747 mm-1, F(000)=2928, the final R= 0.0654 and wR=0.1322 for 3806 observed reflections with I > 2σ(I). In the neutral [Tb(SIP)(H2O)5]2 motif, the Tb(III) ions are linked by the SIP ligands to form a one-dimensional zigzag chain propagating along the c axis. The zigzag chains are linked together by hydrogen bonds and π-π stacking interactions to form a two-dimensional supramolecular framework. The uncoordinated bpy molecules act as pillars to extend the two-dimensional sheets into a distinctive pillared three-dimensional supramolecular structure through O-H···N hydrogen bonds. The photoluminescence of the complex was investigated at room temperature in the solid state.     

Synthesis and Crystal Structure of a Three-dimensional Manganese(II) Complex (tataH)_2[Mn(pydc)_2]·4H_2O (tata = 2,4,6-Triamino-1,3,5-triazine, pydcH_2 = Pyridine-2,6-dicarboxylic Acid)

A manganese(II) complex (tataH)2[Mn(pydc)2]·4H2O (C20H28MnN14O12, Mr = 711.50, tata = 2,4,6-triamino-1,3,5-triazine, pydcH2 = pyridine-2,6-dicarboxylic acid) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1, with a = 9.9847(3), b = 10.9813(3), c = 15.2616(5) , α = 101.5310(10), β = 90.2610(10), γ = 116.4600(10)°, V = 1459.44(8) 3, Z = 2, Dc = 1.619 g/cm3, μ = 0.539 mm–1, F(000) = 734, the final R = 0.0292 and wR = 0.0745. In the crystal the MnII atom is six-coordinated by four carbonyl oxygen atoms and two pyridine nitrogen atoms from two tridentate pydc ligands to furnish a distorted octahedral geometry. The complex shows the A…D…D’…A’ H-bonded tetramer. The molecules are packed in a three-dimensional framework structure by the combination of O–H…O, N–H…O and N–H…N hydrogen bonds between (tataH)+, [Mn(pydc)2]2– and crystal water.     

Synthesis and Crystal Structure of a New Lanthanum（Ⅲ） 4-Cyanobenzoate Complex

A new dinuclear La（Ⅲ） complex [La2（4-cba）4[H（4-cba）2]2（phen）2（H2O）4] （4-Hcba = 4-cyanobenzoic acid and phen = 1,10-phenanthroline） 1 has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by singlecrystal X-ray diffraction. Crystallographic data： C88H58La2N12O20, Mr = 1881.28, triclinic P1, a = 7.518（3）, b = 17.033（6）, c = 17.551（6）A, α = 115.333（4）, β = 92.9910（10）, γ = 99.366（5）°, V = 1985.3（12）A^3, Z = 1, Dc = 1.574 g/cm^3, F（000） = 944 μ = 1.145 mm^–1, the final R = 0.0281 and wR = 0.0686 for 6708 reflections with Ⅰ 〉 2σ（I）. In 1, two nine-coordinated La（Ⅲ） ions are connected by two 4-cba ligands in a syn-syn bidentate coordination mode, and the other six 4-cba ligands terminate the La（Ⅲ） ions, resulting in an isolated dinuclear structure. Two different types of intramolecular hydrogen bonds, asymmetrical O-H…O and symmetrical O…H…O, exist in the crystal. The title complex molecules are connected through hydrogen bonds and weak π-π stacking interactions to generate a 2-D layered network. The thermogravimetric analysis of 1 has also been discussed.     

Synthesis and Structure of a Novel Rare Earth Complex: Eu3(dpa dioxide)4·(CF3COO)5·H2O

The novel europium complex Eu3(dpa dioxide)4·(CF3COO)5·H2O (dpa dioxide = di-2-pyridylamine N,N'-dioxide) was prepared by the reaction of Eu(CF3CO2)3 with Dpa dioxide in acetonitrile under 95 ℃ and determined by X-ray single-crystal diffraction. The crystal belongs to monoclinic system, space group C2/c with a = 41.632(8), b = 14.662(3), c = 23.300(4)(A),β= 100.862(5)°, Z = 8, D = 1.775 g/cm3, V = 13968(4)(A)3, F(000) = 7232, the final R = 0.0464 and wR = 0.1168. In this tri-nuclear complex, each europium(Ⅲ) is nine-coordinated to adopt an unequal sphere geometry.     

Hydrothermal Synthesis,Crystal Structure and Luminescence Property of a New Binuclear Cage-like Samarium(Ⅲ) Complex Sm2(C7H4ClCOO)6(C(12)H8N2)2(H2O)2

A new binuclear cage-like samarium(Ⅲ) complex Sm2(C7H4ClCOO)6(C(12)H8N2)2(H2O)2(1) with samarium(Ⅲ) nitrate, m-chlorobenzoic acid and 1,10-phenanthroline(phen) was synthesized. It crystallizes in the triclinic space group P1, with a = 8.0217(2), b = 12.9037(4), c = 15.3764(5) ?, α = 85.373(3)o, β = 84.396(3)o, γ = 80.443(3)o, V = 1558.64(8) ?~3, Dc = 1.636 g/cm^3, Z = 2, F(000) = 806, the final GOOF = 1.051, R = 0.0754 and wR = 0.1388. The whole molecule consists of two samarium ions bridged by four m-chlorobenzoic acid anions. The Sm(III) ion is coordinated by eight atoms to give a distorted square antiprism coordination geometry. The TG analysis and fluorescent properties of 1 were studied.     

Synthesis and Structure of a Novel Rare Earth Complex: Eu_3(dpa dioxide)_4·(CF_3COO)_5·H_2O

The novel europium complex Eu3(dpa dioxide)4·(CF3COO)5·H2O (dpa dioxide = di-2-pyridylamine N,N'-dioxide) was prepared by the reaction of Eu(CF3CO2)3 with Dpa dioxide in acetonitrile under 95 ℃ and determined by X-ray single-crystal diffraction. The crystal belongs to monoclinic system, space group C2/c with a = 41.632(8), b = 14.662(3), c = 23.300(4) , β = 100.862(5)o, Z = 8, D = 1.775 g/cm3, V = 13968(4) 3, F(000) = 7232, the final R = 0.0464 and wR = 0.1168. In this tri-nuclear complex, each europium(Ⅲ) is nine-coordinated to adopt an unequal sphere geometry.