A new ligand 2-(4,5-dihydro-2-thiazolyl)-6-methoxyl benzothiazole and its new dinuclear Co(II) coordination complex [Co(C11H10N2OS2)Cl2]2·2CHCl3 (1) have been synthesized and characterized. Complex 1 was ...A new ligand 2-(4,5-dihydro-2-thiazolyl)-6-methoxyl benzothiazole and its new dinuclear Co(II) coordination complex [Co(C11H10N2OS2)Cl2]2·2CHCl3 (1) have been synthesized and characterized. Complex 1 was synthesized by the reaction of Co(II) salt with 2-(4,5-dihydro- 2-thiazolyl)-6-methoxyl benzothiazole under room-temperature evaporation condition and struc- turally characterized by single-crystal X-ray diffraction analysis and IR spectroscopy. The supramolecular network of complex 1 is stabilized by the presence of intermolecular interaction, such as C-H···Cl hydrogen bonding and π-π stacking. The complex crystallizes in triclinic, space group P1 with a = 8.3288(12), b = 10.5273(15), c = 10.822(2), α = 93.416(3), β = 90.864(3), γ = 94.890(3)o, V = 943.60(2)3, Z = 2, Dc = 1.758 g/cm3, F(000) = 498 and μ = 1.840 mm-1. The final complex [Co(C11H10N2OS2)Cl2]2·2CHCl3 is a diplex bridged dinuclear complex consisting of two Co(II) ions, two ligands, two bridging Cl- anions and two terminal Cl- anions.展开更多
A new dinuclear copper(II) complex ([Cu(C12H17N2O)(N3)]2, C24H34Cu2N10O2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the monoclinic system, space group P21/c with a =...A new dinuclear copper(II) complex ([Cu(C12H17N2O)(N3)]2, C24H34Cu2N10O2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the monoclinic system, space group P21/c with a = 18.529(4), b = 10.933(2), c = 14.534(3) ?, β = 111.07(3)°, V = 2748(1) ?3, Z = 4, Mr = 621.69, F(000) = 1288, Dc = 1.503 g/cm3 and μ(MoKα) = 1.590 mm?1. The structure was refined to R = 0.0647 and wR = 0.1846 for 4406 observed reflections (I > 2σ(I)). The asymmetric unit comprises two halfmolecules. The complex is a centrosymmetric dimmer in which the copper atoms are penta-coordinated by three coordination atoms from the corresponding tridentate Schiff base ligand and two bridging azide anions. The Cu(II)…Cu(II) average distance is 3.350(1) ?.展开更多
A novel dinuclear complex with an empirical formula [Co2(1H-benzimidazole)4(1, 4-bdoa)2] (1,4-bdoa2– = benzene-1,4-dioxyacetate dianion) has been synthesized and characterized by elemental analysis, IR and single-cry...A novel dinuclear complex with an empirical formula [Co2(1H-benzimidazole)4(1, 4-bdoa)2] (1,4-bdoa2– = benzene-1,4-dioxyacetate dianion) has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. It crystallizes in monoclinic system, space group P21/c with a = 11.000(2), b = 19.385(4), c = 11.417(2) ?, β = 95.49(3)o, V = 2423.3(8) ?3, Z = 2, Mr = 1074.77, Dc = 1.473 g/cm3, μ = 0.760 mm–1, F(000) = 1108, the final R = 0.0645 and wR = 0.0714 for 3273 observed reflections (I > 2σ(I)). Two octahedrally coordinated Co(II) atoms are bridged by two 1,4-bdoa2– groups, generating a macrocyclic ring complex. The Co…Co separa- tion is 7.677(3) ?. An extended 3-D supramolecular network is formed through hydrogen bonds and weak π-π stacking interactions.展开更多
A new neodymiumIII-ironIII complex [Nd(DMSO)5(H2O)2](μ-CN)[Fe(CN)5] (DMSO = dimethyl sulfoxide) has been synthesized by the grinding reaction method. The crystal belongs to monoclinic, space group P21/m with a = 8....A new neodymiumIII-ironIII complex [Nd(DMSO)5(H2O)2](μ-CN)[Fe(CN)5] (DMSO = dimethyl sulfoxide) has been synthesized by the grinding reaction method. The crystal belongs to monoclinic, space group P21/m with a = 8.859(4), b = 13.684(5), c = 12.290(4) ?, ?= 91.85(2)o, C16H34FeN6NdO7S5, Mr= 782.88, V = 1489(1) ?3, Z = 2, Dc = 1.746 g/cm3, S = 0.906, μ(MoKa) = 2.606 mm-1, F(000) = 788, R = 0.0646 and wR = 0.1654. The slightly distorted square-antiprism eightfold-coordinated Nd(III) and approximately oriented octahedrally sixfold- coordinated Fe(III) are linked by a cyano-bridge group to construct a dinuclear compound. The [Nd(DMSO)5(H2O)2](μ-CN)[Fe(CN)5] species are held together via hydrogen bonds to form a three-dimensional framework.展开更多
A new dinuclear copper(II) complex (Cu(C12H17N2O)(NCS)2, C26H34Cu2N6O2S2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic system, space group P1 with a = 11....A new dinuclear copper(II) complex (Cu(C12H17N2O)(NCS)2, C26H34Cu2N6O2S2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic system, space group P1 with a = 11.289(2), b = 12.071(2), c = 12.113(2) ?, α = 72.90(3), β = 83.76(3), γ = 65.60(3)°, V = 1436.7(5) ?3, Z = 2, Mr = 653.79, F(000) = 676, Dc = 1.511 g/cm3, μ(MoKα) = 1.660 mm?1, the final R = 0.0334 and wR = 0.0856 for 5047 observed reflections (I > 2σ(I)). The asymmetric unit comprises two half-molecules. The complex is a centrosymmetric dimmer in which each copper(II) is coordinated in the equatorial plane to the N-(salicylidene)-3- dimethylaminopropylamine ligand through the deprotonated phenolic oxygen atom as well as the nitrogen atoms of imine and amine. The fourth coordination site is occupied by the nitrogen atom of NCS?, while the axial one by the symmetrically related phenoxy oxygen of the other monomeric unit. The Cu(II)…Cu(II) average distance is 3.110(1) ?.展开更多
A novel dinuclear complex [Co2(atr)3(mal)2(H2O)2]·4H2O(1) (atr = 4-amino-1,2,4-triazole and mal = malonic acid) containing mixed N and O-donor atoms has been prepared and structurally characterized. The structure...A novel dinuclear complex [Co2(atr)3(mal)2(H2O)2]·4H2O(1) (atr = 4-amino-1,2,4-triazole and mal = malonic acid) containing mixed N and O-donor atoms has been prepared and structurally characterized. The structure is made up of the symmetrically 1, 2, 4-triazole bridged [Co2(atr)3(mal)2(H2O)2] moiety and four lattice water molecules. The single crystal X-ray analysis reveals that the complex has a distorted octahedral structure. Magnetic susceptibility measurements reveals that antiferromagnetic interactions exists between the high spin Co(II) ions within the dinuclear unit.展开更多
The platinum (II) complexes of the [Pt (N4,N7-Ribavirin) (DMSO) Cl], [Pt (N4,N7-De-oxyribavirin) (DMSO) Cl] were obtained by the reactions of cis-[Pt (DMSO)2 Cl2] and K[Pt (DMSO) Cl3] with 1-??-D-ribofuranosyl-1,2,4-t...The platinum (II) complexes of the [Pt (N4,N7-Ribavirin) (DMSO) Cl], [Pt (N4,N7-De-oxyribavirin) (DMSO) Cl] were obtained by the reactions of cis-[Pt (DMSO)2 Cl2] and K[Pt (DMSO) Cl3] with 1-??-D-ribofuranosyl-1,2,4-triazole-3-carboxamide (Ribavirin) and its deoxy-analogue (deoxyribavirin). The preparation of 1-(2'-deoxy-?-D-ribofuranosyl) -1,2,4-triazole-3-carboxamide was also performed through a four-step procedure, protection of 3', 5'-dihydroxyl group of Ribavirin with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane (TPDS-Cl), phenoxythio-carbonylation of the 2'-hydroxyl group of 3', 5'-O-TPDS-Ribavirin with phenoxythiocarbonyl-chloride (PTC-Cl), reduction of 2′-O-phenoxythiocarbonyl ester of 3', 5'-O-TPDS-Ribavirin with tri-n-butyltin hydride and AIBN, deprotection of 3', 5'-O-TPDS-Ribavirin with tetrabutylammon-ium fluoride in THF.展开更多
An alkaline earth metal-organic framework [Ba(Hsip)(H2O)4]n (1, NaH2sip = 5-sulfoisophthalic acid sodium) has been constructed, and characterized by single-crystal X-ray diffraction. In complex 1, each Ba(II) ...An alkaline earth metal-organic framework [Ba(Hsip)(H2O)4]n (1, NaH2sip = 5-sulfoisophthalic acid sodium) has been constructed, and characterized by single-crystal X-ray diffraction. In complex 1, each Ba(II) atom coordinates to one ligand Hsip3- and four water molecules with a distorted nine-coordinated monocapped tetragonal antiprism geometry. Each Hsip2- anion acts as a μ3-bridging ligand, in which two carboxylate groups adopt the same bidentate chelating coordinating model and the sulfonate group takes a monodentate coordinating model, resulting in a wave-like two-dimensional network with a (6, 3) topological structure. The two-dimensional networks are further linked by O–H···O to form a three-dimensional structure. Luminescent property and thermal stability of complex 1 are investigated. 1 belongs to the orthorhombic system, space group Pna21 with a = 7.3333(2), b = 16.7044(3), c = 10.4817(2), Z = 4, V = 1283.99(5)3, Mr = 453.58, Dc = 2.346 g/cm3, F(000) = 880, μ = 3.314 mm–1, the final R = 0.0261 and wR = 0.0592 for 2425 observed reflections with I 2σ(I).展开更多
Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of th...Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of these complexes in pyridine at different temperature. These complexes could activate molecular oxygen and were used as catalysts in cyclohexene oxidation. The influence of ligand structure on the dioxygen affinity and catalytic activity of the complexes were discussed.展开更多
The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was det...The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.展开更多
A new metal-organic complex Zn2(cbba)4(phen)2 (Hcbba = 2-(4'chlorine-ben- zoyl)benzoic acid, phen = 1,10-phenanthroline) 1 has been hydrothermally synthesized and structurally characterized by elemental analy...A new metal-organic complex Zn2(cbba)4(phen)2 (Hcbba = 2-(4'chlorine-ben- zoyl)benzoic acid, phen = 1,10-phenanthroline) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The compound crystallizes in orthorhombic, space group Pbcn with a = 12.0821(II), b = 18.3140(17), c = 30.961(3) A, V= 6850.7(11) A^3, C80H48C14N4O12Zn2, Mr= 1529.76, Dc = 1.483 g/cm^3,μ(MoKa) = 0.925 mm^-1, F(000) = 3120, Z = 4, the final R = 0.0559 and wR = 0.1146 for 3963 observed reflections (I〉 2σ(I)). In the crystal structure, the zinc atom is five-coordinated with three carboxylate oxygen atoms from three different cbba ligands and two nitrogen atoms from the phen ligand, showing a distorted square-pyramidal geometry. Furthermore, it exhibits a 3D supramolecular network through π-π interactions and shows yellow photoluminescent property at room temperature.展开更多
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 synthe...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.展开更多
A dinuclear complex Cd2(dnba)4(pyridine)4 (dnba = 3,5-dinitrobenzoate) has been synthesized by hydrothermal method and characterized by X-ray single-crystal diffraction, elemental analysis, FT-IR spectroscopy, D...A dinuclear complex Cd2(dnba)4(pyridine)4 (dnba = 3,5-dinitrobenzoate) has been synthesized by hydrothermal method and characterized by X-ray single-crystal diffraction, elemental analysis, FT-IR spectroscopy, DSC and TG-DTG techniques. The complex with empirical formula C48H32Cd2NI2024 (Mr = 692.83) crystallizes in monoclinic, space group P21/n with a - 12.0344(14), b = 10.5752(13), c = 21.578(3) A, β = 104.150(2)°, V = 2662.8(6) A^3, Z = 2, D, = 1.728 g/cm^3,μ(MoKa) = 0.897 mm^-1, F(000) = 1384, S = 1.016 and (△/σ)max = 0.001. R = 0.0638 and wR = 0.0737 for all data; the final R = 0.0337 and wR = 0.0644. In this complex, four carboxylates are bidentate-or chelate-coordinated with the Cd(Ⅱ) centers to give the dinuclear structure. The other coordination positions of Cd(Ⅱ) are occupied by the lone pair electrons from N of four pyridines. Thermal analyses DSC and TG-DTG have been used to determine the thermal decomposition mechanism of the title complex.展开更多
A new zinc(II) complex, Zn(2-NH2py)2Br2 (py=pyridine), has been synthesized, and its molecular structure has been confirmed by IR, elemental analysis and -ray crystal structure analysis. Its space group is P21/n with...A new zinc(II) complex, Zn(2-NH2py)2Br2 (py=pyridine), has been synthesized, and its molecular structure has been confirmed by IR, elemental analysis and -ray crystal structure analysis. Its space group is P21/n with Mr=413.43 (C10H12Br2N4Zn), a=7.435(2), b=12.865(3), c=14.186(4)? b=94.08(2)? V=1353.5(5) 3, Z=4, Dc=2.029 g/cm3, F(000)=328, ?2.378mm-1, R=0.0283, wR=0.0501. The total observed reflections with I≥2?I) were 5314, of which the independent reflections were 3106. The complex structure contains a distorted tetrahedron formed by four atoms coordinated to zinc atom, namely two bromide atoms and two nitrogen atoms. The two ZnBr bond lengths within one molecule, 2.3763(6) and 2.4002(5)? respectively, are not equal; and so are the two ZnN bond lengths, which are 2.031(2) and 2.044(2)?respectively. The calculation results using PM3 method through MOPAC software package in Chem 3D show that its first molecular hyperpolarizability b value is 5.210-30esu, which is comparable with that of p-nitroaniline. No bulk SHG effect has been detected due to the centrosymmetric space group.展开更多
A new dinuclear complex [Zn(dpa)(bipy)(H2O)]2 (dpa = 2,2'-diphenic acid, bipy = 2,2'-bipyridine) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence s...A new dinuclear complex [Zn(dpa)(bipy)(H2O)]2 (dpa = 2,2'-diphenic acid, bipy = 2,2'-bipyridine) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P21/c with a = 10.960(2), b = 9.4841(18), c = 20.599(4), β = 104.452(3)o, V = 2073.4(7)3, C48H36N4O10Zn2, Mr = 959.55, Dc = 1.537 g/cm3, μ(MoKα) = 1.225 mm-1, F(000) = 984, Z = 2, the final R = 0.0364 and wR = 0.0843 for 2788 observed reflections (I 〉 2σ(I)). In the crystal structure, the zinc atom is five-coordinated with two carboxylate oxygen atoms from different dpas, one coordinated water molecule and two nitrogen atoms from bipy ligands, showing a slightly distorted triangular bipyramidal geometry. Furthermore, it exhibits a zero-dimensional network structure with a sixteen-membered ring and shows yellow photoluminescent property at room temperature.展开更多
A new dinuclear manganese complex [Mn2(L)2(2,2'-bipy)2(H2O)512·3H2O has been synthesized with MnSO4·H2O, 2,2'-bibenzoic acid (H2L) and 2,2'-bipyridine(2,2'-bipy) in the mixed solvent ethanol an...A new dinuclear manganese complex [Mn2(L)2(2,2'-bipy)2(H2O)512·3H2O has been synthesized with MnSO4·H2O, 2,2'-bibenzoic acid (H2L) and 2,2'-bipyridine(2,2'-bipy) in the mixed solvent ethanol and water. It crystallizes in monoclinic, space group Pi with a = 9.9944(10), b = 21.939(2), c = 25.628(3) A, a = 108.429(3), β = 100.613(4), 7 = 102.821(3)°, V = 4997.9(9) A3, Dc= 1.355 g/cm^3, Z = 2, F(000) = 2108, GOOF = 1.074, the R= 0.0626 and wR= 0.1531. The structure of the complex contains two [Mn2(L)2(2,2'-bipy)2] units, ten coordinated H2O molecules and three uncoordinated H2O molecules. The fluorescence, thermal stability and magnetic properties of the complex were investigated.展开更多
A new dinuclear copper(II) complex [Cu2(L)2(phen)2]·5H2O (1) with bicycle[2.2.1 ]hept- 2-en-5, 6-dicarboxylic acid (H2L) and 1,10-phenanthroline (phen) as ligands has been synthesized in the mixed sol...A new dinuclear copper(II) complex [Cu2(L)2(phen)2]·5H2O (1) with bicycle[2.2.1 ]hept- 2-en-5, 6-dicarboxylic acid (H2L) and 1,10-phenanthroline (phen) as ligands has been synthesized in the mixed solvents of ethanol and water. It crystallizes in the monoclinic space group P21/c, with a = 17.925(4), b = 19.908(4), c = 11.235(2) A, β = 97.65(3)°, V= 3973.4(14) A3, Dc = 1.552 g/cm^3, Z = 8, F(000) = 1910, the final GOOF = 1.056, R= 0.0519 and wR= 0.1293. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two copper ions are bridged by twoμ2-η1 :η0-3-carboxylate groups of L^2- anions. The fluorescence and thermal stability properties of 1 were studied. The results show that 1 has an intense fluorescent emission at around 381 rim. The TG analysis shows that I is stable below 143 ℃.展开更多
Two homochiral mercury (1) and cadmium (2) complexes derived from chiral twisted biphenyl pyridine ligand (3,3'-bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl) have been synthesized and chara...Two homochiral mercury (1) and cadmium (2) complexes derived from chiral twisted biphenyl pyridine ligand (3,3'-bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl) have been synthesized and characterized by IR, microanalysis, TGA, UV-Vis, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 2. For 1, a = 14.2038(16), b = 14.3630(17), c = 7.0257(8), V = 1433.3(3)3, Mr = 878.91, Dc = 2.037 g/cm3, μ = 7.549 mm-1, F(000) = 824, the final GOF = 1.017, R = 0.0296 and wR = 0.0645 for 2925 observed reflections with I 2σ(I). For 2, a = 14.212(3), b = 14.392(3), c = 7.0498(14), V = 1442.0(5)3, Mr = 790.72, Dc = 1.821 g/cm3, μ = 2.924 mm–1, F(000) = 760, the final GOF = 1.075, R = 0.0340 and wR = 0.0834 for 3144 observed reflections with I 2σ(I). The crystal structures of 1 and 2 are isostructural and each adopts a two-dimensional supramolecular network which contains the C–H···π interactions.展开更多
A mixed-valence dinuclear manganese complex, [Mn ⅡMn ⅢL](ClO 4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)...A mixed-valence dinuclear manganese complex, [Mn ⅡMn ⅢL](ClO 4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)-2-hydroxybenzyl amine, was obtained and its structure was determined by X-ray diffraction. The orange crystal is a monoclinic system with space group P2 1/c and lattice parameters a=1.1617(4), b=1.4005(3), c=1.4641(3) nm, β=113.03(2)°, and Z=2. The crystal structure shows that each pendant-arm is bonded in a bidentate fashion to the adjacent metal atom and that both the arms are on the same side of the macrocycle. The two Mn atoms are bridged by two μ 2-phenoxy oxygen atoms of the tetra-imine macrocycle, and each Mn atom, locating in a trigonal prismatic coordination environment(N 3O 3), is six-coordinated by the two imine nitrogen atoms, one tertiary nitrogen atom and a pendant phenol moiety apart from the two oxygen atoms.展开更多
A new 4-chlorobenzoic acid bridge Co(Ⅱ ) complex [[Co2(2,2'-bpy)2(μ-L)e(L)2(μ-H2O)] (HL = 4-chlorobenzoic acid) has been obtained by hydrothermal synthesis, and X-ray single-crystal diffraction analysi...A new 4-chlorobenzoic acid bridge Co(Ⅱ ) complex [[Co2(2,2'-bpy)2(μ-L)e(L)2(μ-H2O)] (HL = 4-chlorobenzoic acid) has been obtained by hydrothermal synthesis, and X-ray single-crystal diffraction analysis shows that it crystallizes in the monoclinic system, space group C2/c with a = 22.537(5), b = 16.212(3), c = 15.306(3) A, β= 124.37(3)°, V= 4616.1(16)A3, Mr = 1070.45, Dc = 1.540 g/cm3, Z = 4, p = 1.012 mm-1, F(000) = 2176, the final R = 0.0338 and wR= 0.0810. The title complex is composed of dinuclear [Co2(2,2'-bpy)2(μ-L)2(L)2(μ-HaO)] molecules. Each Co(Ⅱ ) atom is coordinated by two nitrogen atoms from one 2,2’-bipyridine ligand, three oxygen atoms from three 4-chlorobenzoic ions and another oxygen atom from one water molecule. The two Co(Ⅱ) atoms are connected by two 4-chlorobenzoic ions and one bridged water molecule. The dinuclear molecules are interlinked by hydrogen bond and π-π stacking interactions into a three-dimensional supramolecular network.展开更多
基金supported by the National Natural Science Foundation of China (No. 20972124)the China Postdoctoral Science Foundation (No. 20080441180)the Natural Science Foundation of Shaanxi Province (No. 2007B04)
文摘A new ligand 2-(4,5-dihydro-2-thiazolyl)-6-methoxyl benzothiazole and its new dinuclear Co(II) coordination complex [Co(C11H10N2OS2)Cl2]2·2CHCl3 (1) have been synthesized and characterized. Complex 1 was synthesized by the reaction of Co(II) salt with 2-(4,5-dihydro- 2-thiazolyl)-6-methoxyl benzothiazole under room-temperature evaporation condition and struc- turally characterized by single-crystal X-ray diffraction analysis and IR spectroscopy. The supramolecular network of complex 1 is stabilized by the presence of intermolecular interaction, such as C-H···Cl hydrogen bonding and π-π stacking. The complex crystallizes in triclinic, space group P1 with a = 8.3288(12), b = 10.5273(15), c = 10.822(2), α = 93.416(3), β = 90.864(3), γ = 94.890(3)o, V = 943.60(2)3, Z = 2, Dc = 1.758 g/cm3, F(000) = 498 and μ = 1.840 mm-1. The final complex [Co(C11H10N2OS2)Cl2]2·2CHCl3 is a diplex bridged dinuclear complex consisting of two Co(II) ions, two ligands, two bridging Cl- anions and two terminal Cl- anions.
文摘A new dinuclear copper(II) complex ([Cu(C12H17N2O)(N3)]2, C24H34Cu2N10O2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the monoclinic system, space group P21/c with a = 18.529(4), b = 10.933(2), c = 14.534(3) ?, β = 111.07(3)°, V = 2748(1) ?3, Z = 4, Mr = 621.69, F(000) = 1288, Dc = 1.503 g/cm3 and μ(MoKα) = 1.590 mm?1. The structure was refined to R = 0.0647 and wR = 0.1846 for 4406 observed reflections (I > 2σ(I)). The asymmetric unit comprises two halfmolecules. The complex is a centrosymmetric dimmer in which the copper atoms are penta-coordinated by three coordination atoms from the corresponding tridentate Schiff base ligand and two bridging azide anions. The Cu(II)…Cu(II) average distance is 3.350(1) ?.
基金This work was supported by the National Natural Science Foundation of China (No. 20101003), Natural Science Foundation of Heilongjiang Province (No. B0007) and the Scientific Fund of Remarkable Teachers of Heilongjiang Province (1054G036)
文摘A novel dinuclear complex with an empirical formula [Co2(1H-benzimidazole)4(1, 4-bdoa)2] (1,4-bdoa2– = benzene-1,4-dioxyacetate dianion) has been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. It crystallizes in monoclinic system, space group P21/c with a = 11.000(2), b = 19.385(4), c = 11.417(2) ?, β = 95.49(3)o, V = 2423.3(8) ?3, Z = 2, Mr = 1074.77, Dc = 1.473 g/cm3, μ = 0.760 mm–1, F(000) = 1108, the final R = 0.0645 and wR = 0.0714 for 3273 observed reflections (I > 2σ(I)). Two octahedrally coordinated Co(II) atoms are bridged by two 1,4-bdoa2– groups, generating a macrocyclic ring complex. The Co…Co separa- tion is 7.677(3) ?. An extended 3-D supramolecular network is formed through hydrogen bonds and weak π-π stacking interactions.
基金The project was supported by NNSFC (20001007 20131020) and NSF of the Chinese Academy of Sciences (KJCX2-H3) and Fujian Province (2000F006)
文摘A new neodymiumIII-ironIII complex [Nd(DMSO)5(H2O)2](μ-CN)[Fe(CN)5] (DMSO = dimethyl sulfoxide) has been synthesized by the grinding reaction method. The crystal belongs to monoclinic, space group P21/m with a = 8.859(4), b = 13.684(5), c = 12.290(4) ?, ?= 91.85(2)o, C16H34FeN6NdO7S5, Mr= 782.88, V = 1489(1) ?3, Z = 2, Dc = 1.746 g/cm3, S = 0.906, μ(MoKa) = 2.606 mm-1, F(000) = 788, R = 0.0646 and wR = 0.1654. The slightly distorted square-antiprism eightfold-coordinated Nd(III) and approximately oriented octahedrally sixfold- coordinated Fe(III) are linked by a cyano-bridge group to construct a dinuclear compound. The [Nd(DMSO)5(H2O)2](μ-CN)[Fe(CN)5] species are held together via hydrogen bonds to form a three-dimensional framework.
文摘A new dinuclear copper(II) complex (Cu(C12H17N2O)(NCS)2, C26H34Cu2N6O2S2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the triclinic system, space group P1 with a = 11.289(2), b = 12.071(2), c = 12.113(2) ?, α = 72.90(3), β = 83.76(3), γ = 65.60(3)°, V = 1436.7(5) ?3, Z = 2, Mr = 653.79, F(000) = 676, Dc = 1.511 g/cm3, μ(MoKα) = 1.660 mm?1, the final R = 0.0334 and wR = 0.0856 for 5047 observed reflections (I > 2σ(I)). The asymmetric unit comprises two half-molecules. The complex is a centrosymmetric dimmer in which each copper(II) is coordinated in the equatorial plane to the N-(salicylidene)-3- dimethylaminopropylamine ligand through the deprotonated phenolic oxygen atom as well as the nitrogen atoms of imine and amine. The fourth coordination site is occupied by the nitrogen atom of NCS?, while the axial one by the symmetrically related phenoxy oxygen of the other monomeric unit. The Cu(II)…Cu(II) average distance is 3.110(1) ?.
文摘A novel dinuclear complex [Co2(atr)3(mal)2(H2O)2]·4H2O(1) (atr = 4-amino-1,2,4-triazole and mal = malonic acid) containing mixed N and O-donor atoms has been prepared and structurally characterized. The structure is made up of the symmetrically 1, 2, 4-triazole bridged [Co2(atr)3(mal)2(H2O)2] moiety and four lattice water molecules. The single crystal X-ray analysis reveals that the complex has a distorted octahedral structure. Magnetic susceptibility measurements reveals that antiferromagnetic interactions exists between the high spin Co(II) ions within the dinuclear unit.
文摘The platinum (II) complexes of the [Pt (N4,N7-Ribavirin) (DMSO) Cl], [Pt (N4,N7-De-oxyribavirin) (DMSO) Cl] were obtained by the reactions of cis-[Pt (DMSO)2 Cl2] and K[Pt (DMSO) Cl3] with 1-??-D-ribofuranosyl-1,2,4-triazole-3-carboxamide (Ribavirin) and its deoxy-analogue (deoxyribavirin). The preparation of 1-(2'-deoxy-?-D-ribofuranosyl) -1,2,4-triazole-3-carboxamide was also performed through a four-step procedure, protection of 3', 5'-dihydroxyl group of Ribavirin with 1,3-dichloro-1,1,3,3-tetraisopropyldisiloxane (TPDS-Cl), phenoxythio-carbonylation of the 2'-hydroxyl group of 3', 5'-O-TPDS-Ribavirin with phenoxythiocarbonyl-chloride (PTC-Cl), reduction of 2′-O-phenoxythiocarbonyl ester of 3', 5'-O-TPDS-Ribavirin with tri-n-butyltin hydride and AIBN, deprotection of 3', 5'-O-TPDS-Ribavirin with tetrabutylammon-ium fluoride in THF.
基金supported by the University Science Foundation of Anhui Province (No. KJ2011Z271)the Applied Chemistry Key Constructing Subject of Anhui Province (No. 200802187C)
文摘An alkaline earth metal-organic framework [Ba(Hsip)(H2O)4]n (1, NaH2sip = 5-sulfoisophthalic acid sodium) has been constructed, and characterized by single-crystal X-ray diffraction. In complex 1, each Ba(II) atom coordinates to one ligand Hsip3- and four water molecules with a distorted nine-coordinated monocapped tetragonal antiprism geometry. Each Hsip2- anion acts as a μ3-bridging ligand, in which two carboxylate groups adopt the same bidentate chelating coordinating model and the sulfonate group takes a monodentate coordinating model, resulting in a wave-like two-dimensional network with a (6, 3) topological structure. The two-dimensional networks are further linked by O–H···O to form a three-dimensional structure. Luminescent property and thermal stability of complex 1 are investigated. 1 belongs to the orthorhombic system, space group Pna21 with a = 7.3333(2), b = 16.7044(3), c = 10.4817(2), Z = 4, V = 1283.99(5)3, Mr = 453.58, Dc = 2.346 g/cm3, F(000) = 880, μ = 3.314 mm–1, the final R = 0.0261 and wR = 0.0592 for 2425 observed reflections with I 2σ(I).
文摘Oxygenation constants and thermodynamic parameters DeltaH degrees and DeltaS degrees of cobalt (II) complexes with bis-(furaldehyde) Schiff bases (1, 2, 3, 4)were obtained by mearsuring saturated dioxygen uptake of these complexes in pyridine at different temperature. These complexes could activate molecular oxygen and were used as catalysts in cyclohexene oxidation. The influence of ligand structure on the dioxygen affinity and catalytic activity of the complexes were discussed.
基金This work was supported by the National Natural Science Foundation of China (20001007 20131020)+1 种基金and Natural Science Foundation of Fujian Province (2003I031 A0420002)
文摘The title complex [Cu2(bipy)2(Hpht)2Cl](Hpht) (bipy = 2,2?-bipyridine, H2pht = o-phthalic acid) has been synthesized in the NaOH aqueous solution of CuCl2, Gd(NO3)3, bipy and H2pht, and its crystal structure was determined by single-crystal X-ray diffraction method. It crys- tallizes in triclinic, space group P1, C44H31ClCu2N4O12, Mr = 970.26, a = 8.175(2), b = 16.254(4), c = 16.946(4) ?, α = 62.966(6), β = 84.833(8), γ = 84.348(8)°, V = 1993.4(8) ?3, Z = 2, Dc = 1.616 g/cm3, F(000) = 988 and μ = 1.207 mm-1. The final R = 0.0429 and wR = 0.0843 for 5682 observed reflections with I > 2σ(I). Each copper(II) atom displays a distorted square-pyramidal geometry with two nitrogen atoms of one chelate 2,2?-bipy molecule, two oxygen atoms from two different bridging carboxylate groups of Hpht- and one bridging chloride atom occupying the apical position. The two copper(II) atoms are connected by a μ2-Cl atom and two bridging Hpht- ligands in a syn-syn coordination mode to form an isolated dinuclear unit. The molecular structure is extended to a one-dimensional wavy chain through hydrogen bonds. The title complex exhibits blue fluorescent emission at 443 nm (λex = 372 nm) in the solid state at room temperature.
基金supported by the Science and Technology Research Projects of the Education Department of Jilin Province (No. 2011. 459)
文摘A new metal-organic complex Zn2(cbba)4(phen)2 (Hcbba = 2-(4'chlorine-ben- zoyl)benzoic acid, phen = 1,10-phenanthroline) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The compound crystallizes in orthorhombic, space group Pbcn with a = 12.0821(II), b = 18.3140(17), c = 30.961(3) A, V= 6850.7(11) A^3, C80H48C14N4O12Zn2, Mr= 1529.76, Dc = 1.483 g/cm^3,μ(MoKa) = 0.925 mm^-1, F(000) = 3120, Z = 4, the final R = 0.0559 and wR = 0.1146 for 3963 observed reflections (I〉 2σ(I)). In the crystal structure, the zinc atom is five-coordinated with three carboxylate oxygen atoms from three different cbba ligands and two nitrogen atoms from the phen ligand, showing a distorted square-pyramidal geometry. Furthermore, it exhibits a 3D supramolecular network through π-π interactions and shows yellow photoluminescent property at room temperature.
基金Supported by the Natural Science Foundation of Zhejiang Province (Y407301)
文摘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.
基金The project was supported by the National Natural Science Foundation of China (20471008) and the Fundamental Research Foundation of Beijing Institute of Technology (BIT-UBF-200302B01&BIT-UBF-200502B4221)
文摘A dinuclear complex Cd2(dnba)4(pyridine)4 (dnba = 3,5-dinitrobenzoate) has been synthesized by hydrothermal method and characterized by X-ray single-crystal diffraction, elemental analysis, FT-IR spectroscopy, DSC and TG-DTG techniques. The complex with empirical formula C48H32Cd2NI2024 (Mr = 692.83) crystallizes in monoclinic, space group P21/n with a - 12.0344(14), b = 10.5752(13), c = 21.578(3) A, β = 104.150(2)°, V = 2662.8(6) A^3, Z = 2, D, = 1.728 g/cm^3,μ(MoKa) = 0.897 mm^-1, F(000) = 1384, S = 1.016 and (△/σ)max = 0.001. R = 0.0638 and wR = 0.0737 for all data; the final R = 0.0337 and wR = 0.0644. In this complex, four carboxylates are bidentate-or chelate-coordinated with the Cd(Ⅱ) centers to give the dinuclear structure. The other coordination positions of Cd(Ⅱ) are occupied by the lone pair electrons from N of four pyridines. Thermal analyses DSC and TG-DTG have been used to determine the thermal decomposition mechanism of the title complex.
基金This work was financed by the National Key Fundamental Research Program of China.
文摘A new zinc(II) complex, Zn(2-NH2py)2Br2 (py=pyridine), has been synthesized, and its molecular structure has been confirmed by IR, elemental analysis and -ray crystal structure analysis. Its space group is P21/n with Mr=413.43 (C10H12Br2N4Zn), a=7.435(2), b=12.865(3), c=14.186(4)? b=94.08(2)? V=1353.5(5) 3, Z=4, Dc=2.029 g/cm3, F(000)=328, ?2.378mm-1, R=0.0283, wR=0.0501. The total observed reflections with I≥2?I) were 5314, of which the independent reflections were 3106. The complex structure contains a distorted tetrahedron formed by four atoms coordinated to zinc atom, namely two bromide atoms and two nitrogen atoms. The two ZnBr bond lengths within one molecule, 2.3763(6) and 2.4002(5)? respectively, are not equal; and so are the two ZnN bond lengths, which are 2.031(2) and 2.044(2)?respectively. The calculation results using PM3 method through MOPAC software package in Chem 3D show that its first molecular hyperpolarizability b value is 5.210-30esu, which is comparable with that of p-nitroaniline. No bulk SHG effect has been detected due to the centrosymmetric space group.
基金Supported by the Science and Technology Research Projects of the Education Office of Jilin Province (No. 2009. 272)
文摘A new dinuclear complex [Zn(dpa)(bipy)(H2O)]2 (dpa = 2,2'-diphenic acid, bipy = 2,2'-bipyridine) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P21/c with a = 10.960(2), b = 9.4841(18), c = 20.599(4), β = 104.452(3)o, V = 2073.4(7)3, C48H36N4O10Zn2, Mr = 959.55, Dc = 1.537 g/cm3, μ(MoKα) = 1.225 mm-1, F(000) = 984, Z = 2, the final R = 0.0364 and wR = 0.0843 for 2788 observed reflections (I 〉 2σ(I)). In the crystal structure, the zinc atom is five-coordinated with two carboxylate oxygen atoms from different dpas, one coordinated water molecule and two nitrogen atoms from bipy ligands, showing a slightly distorted triangular bipyramidal geometry. Furthermore, it exhibits a zero-dimensional network structure with a sixteen-membered ring and shows yellow photoluminescent property at room temperature.
基金Supported by the Key Project of Science and Technology Plan of Hunan Province(2012FJ2002)Science and Technology Committee of Hengyang(2013KG77)the Construct Program of the Key Discipline in Hunan Province
文摘A new dinuclear manganese complex [Mn2(L)2(2,2'-bipy)2(H2O)512·3H2O has been synthesized with MnSO4·H2O, 2,2'-bibenzoic acid (H2L) and 2,2'-bipyridine(2,2'-bipy) in the mixed solvent ethanol and water. It crystallizes in monoclinic, space group Pi with a = 9.9944(10), b = 21.939(2), c = 25.628(3) A, a = 108.429(3), β = 100.613(4), 7 = 102.821(3)°, V = 4997.9(9) A3, Dc= 1.355 g/cm^3, Z = 2, F(000) = 2108, GOOF = 1.074, the R= 0.0626 and wR= 0.1531. The structure of the complex contains two [Mn2(L)2(2,2'-bipy)2] units, ten coordinated H2O molecules and three uncoordinated H2O molecules. The fluorescence, thermal stability and magnetic properties of the complex were investigated.
基金Supported by the Construct Program of the Key Discipline in Hunan Province and Key Project of Production Plan of Hengyang City(2013)
文摘A new dinuclear copper(II) complex [Cu2(L)2(phen)2]·5H2O (1) with bicycle[2.2.1 ]hept- 2-en-5, 6-dicarboxylic acid (H2L) and 1,10-phenanthroline (phen) as ligands has been synthesized in the mixed solvents of ethanol and water. It crystallizes in the monoclinic space group P21/c, with a = 17.925(4), b = 19.908(4), c = 11.235(2) A, β = 97.65(3)°, V= 3973.4(14) A3, Dc = 1.552 g/cm^3, Z = 8, F(000) = 1910, the final GOOF = 1.056, R= 0.0519 and wR= 0.1293. The crystal structure shows that the whole molecule consists of two independent dinuclear units, in which two copper ions are bridged by twoμ2-η1 :η0-3-carboxylate groups of L^2- anions. The fluorescence and thermal stability properties of 1 were studied. The results show that 1 has an intense fluorescent emission at around 381 rim. The TG analysis shows that I is stable below 143 ℃.
基金supported by NNSFC (20971085)"973" Programs (2007CB209701 and 2009CB930403)the Key Project and Scientific Research Foundation for the Returned Overseas Chinese Scholars of State Education Ministry
文摘Two homochiral mercury (1) and cadmium (2) complexes derived from chiral twisted biphenyl pyridine ligand (3,3'-bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl) have been synthesized and characterized by IR, microanalysis, TGA, UV-Vis, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 2. For 1, a = 14.2038(16), b = 14.3630(17), c = 7.0257(8), V = 1433.3(3)3, Mr = 878.91, Dc = 2.037 g/cm3, μ = 7.549 mm-1, F(000) = 824, the final GOF = 1.017, R = 0.0296 and wR = 0.0645 for 2925 observed reflections with I 2σ(I). For 2, a = 14.212(3), b = 14.392(3), c = 7.0498(14), V = 1442.0(5)3, Mr = 790.72, Dc = 1.821 g/cm3, μ = 2.924 mm–1, F(000) = 760, the final GOF = 1.075, R = 0.0340 and wR = 0.0834 for 3144 observed reflections with I 2σ(I). The crystal structures of 1 and 2 are isostructural and each adopts a two-dimensional supramolecular network which contains the C–H···π interactions.
基金the Natural Science Foundation of Shandong Province(No.Y2 0 0 2 B0 6 )
文摘A mixed-valence dinuclear manganese complex, [Mn ⅡMn ⅢL](ClO 4)·1/2MeOH, where L is a macrocyclic ligand derived from the cyclocondensation of sodium 2,6-diformyl-4-methylphenolate with N,N-bis(2-aminoethyl)-2-hydroxybenzyl amine, was obtained and its structure was determined by X-ray diffraction. The orange crystal is a monoclinic system with space group P2 1/c and lattice parameters a=1.1617(4), b=1.4005(3), c=1.4641(3) nm, β=113.03(2)°, and Z=2. The crystal structure shows that each pendant-arm is bonded in a bidentate fashion to the adjacent metal atom and that both the arms are on the same side of the macrocycle. The two Mn atoms are bridged by two μ 2-phenoxy oxygen atoms of the tetra-imine macrocycle, and each Mn atom, locating in a trigonal prismatic coordination environment(N 3O 3), is six-coordinated by the two imine nitrogen atoms, one tertiary nitrogen atom and a pendant phenol moiety apart from the two oxygen atoms.
基金supported by the Science and Technology Bureau of Jinhua City (No. 2003-01-179)
文摘A new 4-chlorobenzoic acid bridge Co(Ⅱ ) complex [[Co2(2,2'-bpy)2(μ-L)e(L)2(μ-H2O)] (HL = 4-chlorobenzoic acid) has been obtained by hydrothermal synthesis, and X-ray single-crystal diffraction analysis shows that it crystallizes in the monoclinic system, space group C2/c with a = 22.537(5), b = 16.212(3), c = 15.306(3) A, β= 124.37(3)°, V= 4616.1(16)A3, Mr = 1070.45, Dc = 1.540 g/cm3, Z = 4, p = 1.012 mm-1, F(000) = 2176, the final R = 0.0338 and wR= 0.0810. The title complex is composed of dinuclear [Co2(2,2'-bpy)2(μ-L)2(L)2(μ-HaO)] molecules. Each Co(Ⅱ ) atom is coordinated by two nitrogen atoms from one 2,2’-bipyridine ligand, three oxygen atoms from three 4-chlorobenzoic ions and another oxygen atom from one water molecule. The two Co(Ⅱ) atoms are connected by two 4-chlorobenzoic ions and one bridged water molecule. The dinuclear molecules are interlinked by hydrogen bond and π-π stacking interactions into a three-dimensional supramolecular network.