Hydrothermal Synthesis,Crystal Structure and Magnetic Behavior of a Novel 3D Supramolecular Complex [Cu（HDPPZC）（SO4）（H2 O）]2

In the title coordination compound,[Cu(HDPPZC)(SO4)(H2O)]2 (1,HDPPZC=dipyrido[3,2-a:2,3-c]-phenazine-2-carboxylic acid),has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction,elemental analysis and magnetic susceptibility measurement.It crystallizes in triclinic,space group P1 with a=0.69485(6),b=0.76878(4),c=1.76638(13)nm,α=99.437(6),β=94.690(6),γ=95.735(6)o,V=0.92151(12) nm 3,Z=1,Cu2C38 H24 N 8S2O14,Mr=1007.85,Dc= 1.816 g·cm-3,F(000)=510,GOOF=0.988,the final R=0.0580 and wR=0.0689.The structural analyses reveal that complex 1 shows discrete dinuclear clusters,which are further linked by hydrogen bonding and π·π stacking interactions to form a three-dimensional supramolecular compound.Magnetic measurement shows ferromagnetic and antiferromagnetic exchange interactions in the sample.     

Cadmium（Ⅱ） Nitrite Complex Based on the Bis（2-benzimidazole） and Aromatic Carboxylate Ligands

A new cadmium(Ⅱ) nitrite complex Cd2(H2C3PIm)2(BDC)(NO2)2(1,H2C3PIm = 2,2'-(1,3-propanediyl)bis(1H-benzimidazole),H2BDC = 1,4-benzenedicarboxylic acid) has been synthesized by solvothermal reaction in formamide,and its structure(C42H36Cd2N10O8,Mr = 1033.61) was determined by single-crystal X-ray diffraction analysis.The crystal belongs to the monoclinic system,space group P21/n with a = 0.9859(5),b = 0.8936(5),c = 2.3188(5) nm,β = 97.576(5)°,V = 2.025(16) nm3,Z = 2,Dc = 1.695 g/cm3,μ(MoKα) = 1.118 mm-1,F(000) = 1036,S = 1.017,the final R = 0.0304 and wR = 0.0752 for 3761 reflections with I > 2σ(I).The centrosymmetric complex 1 contains a dimer in which two distorted octahedral Cd(II) centers are bridged by BDC ligand and chelated by H2C3PIm.The units of the complex are linked via weak N-H···O hydrogen bonds between the nitrito and the BDC ligands,leading to the formation of a 1D zigzag chain along the b axis.The π-π packing interactions contribute to the formation of a three-dimensional supramolecular architecture.The complex exhibits strong photoluminescence at room temperature.     

Theoretical Studies on the Molecular Structures and Thermodynamic Properties of Polychlorinated Fluoranthenes

DFT-B3LYP/6-311G** method has been used to optimize molecular geometric structures of 527 polychlorinated fluoranthene(PCFRT) congeners and calculate their thermo-dynamic properties in the ideal gas state,such as heat capacity at constant volume(Cv),entropy(S),standard enthalpy of formation(ΔfH) and standard Gibbs free energy of formation(ΔfG).The relations of Cv,S,ΔfH and ΔfG with the number and position of chlorine atoms have also been explored,from which the relative stability of PCFRT congeners was theoretically proposed according to the magnitude of the relative standard Gibbs free energy of formation(Δr,fG).It was found that some of the PCFRT isomers are in a nonplanar configuration and there are intramolecular Cl…Cl weak interactions in some of the isomers.With increasing the number of chlorine atoms,the values of ΔfH and ΔfG of the most stable PCFRT isomers decrease initially and then increase.The values of ΔfH and ΔfG of PCFRT congeners with the same number of chlorine atoms show a strong dependence on the positions of chlorine atoms.The relative thermodynamic stability of PCFRT isomers is determined mainly by intramolecular adjacent Cl…Cl nuclear repulsive interaction between Cl atoms at two different six-membered rings.Most PCFRT congeners are easier to form thermodynamically than their parent compound.     

Synthesis,Crystal Structure and Cytotoxic Activity of a Zinc（Ⅱ） Complex of the Schiff Base Derived from S-benzyldithiocarbazate

A novel zinc(Ⅱ) complex of empirical formula,ZnL2(L=anionic forms of S-benzyl-β-N-(2,4-dichlorobenzylidene) hydrazine carbodithioate),has been synthesized and characterized by elemental analysis,IR spectra and single-crystal X-ray diffraction.The crystal belongs to the triclinic system,space group P with a = 9.3168(9),b = 13.0353(13),c = 14.7702(15) ,α = 71.2860(10),= 87.5140(10),γ = 79.4480(10)o,V = 1670.0(3) 3,Z = 2,Mr = 773.93,Dc = 1.539 g/cm3,μ = 1.334 mm-1,F(000) = 784,the final R = 0.0403 and wR = 0.0800 for 4060 observed reflections with I>2(I).In the crystal structure,the zinc(Ⅱ) complex has a distorted tetrahedral geometry in which the zinc ion is coordinated by the nitrogen and sulfur atoms from two Schiff base ligands,respectively.The preliminary bioassay indicates that the Schiff base and its zinc complex exhibit inhibitory activity against the human gastric cancer cell lines(MKN45) and hepatoma cell lines(HepG2).     

Urothermal Synthesis and Crystal Structure of a Zn（Ⅱ） Coordination Polymer with a 3-D Supramolecular Structure

A new metal-organic coordination polymer [Zn(hfipbb)(e-urea)]n(1,H2hfipbb = 4,4'-(hexafluoroisopropylidene)bis(benzoic acid),e-urea = ethylene urea) has been urothermally synthesized and characterized by elemental analysis and single-crystal X-ray diffraction.The title complex crystallizes in monoclinic,space group P21/c with a = 13.302(4),b = 10.981(3),c = 13.804(4) ,β = 93.587(5)°,V = 2012.3(10) 3,C20H14N2O5F6Zn,Mr = 541.72,Z = 4,Dc = 0.447 g/cm3, = 0.328 mm-1,F(000) = 272,R = 0.0340 and wR = 0.1107 for 4528 observed reflections(I >2σ(I)).In the structure of compound 1,two Zn(Ⅱ) ions are bridged by two carboxylate groups from two hfipbb ligands to form a dinuclear unit,and each dinuclear Zn(Ⅱ) unit is linked with its two adjacent dinuclear units through four hfipbb ligands into an infinite one-dimensional double-chain.The interesting structural feature of compound 1 is that the one-D double-chains are self-interconnected into a three-D supramolecular structure through hydrogen bonds between the coordinated e-urea molecules and carboxylate oxygen atoms(N1 and O2,N2 and O4).     

Syntheses and Single-crystal Structures of Ln_3Sn_(0.25)GeS_7 (Ln=La,Sm)

Two new quaternary sulfides,La3Sn0.25GeS71 and Sm3 Sn0.25GeS72,have been synthesized by a facile solid-state reaction,and their crystal structures were determined by singlecrystal X-ray diffraction analysis.The two compounds crystallize in the P6 3 space group,and the crystal data are as follows-La3Sn0.25GeS7:a=10.3335(7),c=5.8455(7),Z=2;Sm3Sn0.25GeS7:a=9.999(3),c=5.787(2),Z=2.Single-crystal analysis indicated that the two compounds consist of three types of building blocks:LnS 8 anti-tetragonal prism,SnS 6 octahedron,and GeS 4 tetrahedron.     

Synthesis,Structure and Fluorescence Study of 3-Bromo-7-methyloxy-4-methylcoumarin

Coumarin derivative 3-bromo-7-methyloxy-4-methylcoumarin(C11H9BrO3) was synthesized and characterized by FT-IR,1H NMR spectra,and thermal analysis.The crystal structure was determined by X-ray single-crystal diffraction.The title compound crystallizes in the mono-clinic system,space group P21/n,with a = 7.770(16),b = 12.501(3),c = 10.627(2),β = 98.46(3)°,Mr = 269.09,V = 1021.0(4) 3,Z = 4,Dc = 1.751 g/cm3,μ = 4.008 mm-1,F(000) = 536,R = 0.0650 and wR = 0.1463.The optimization of the title compound was obtained by quantum chemical method at the SVWN5/6-31G** level.In the structure,the measured angles of the crystal structure are similar to those calculated,while the measured bond lengths are shorter than the calculated values due to the crystal field which functions to the molecule.The title compound also shows good fluorescent behaviors and good linear relationship with the equal concentration gradient in methanol.     

Synthesis and Structural Features of 3,5-Dihydroxy N′-(3-nitrobenzylidene) Benzohydrazide and Its Effect on the Intestinal Smooth Muscle

A new compound,3,5-dihydroxy-N-(3-nitrobenzylidene)benzohydrazide (DNBB) methanol solvate,was synthesized and characterized by single-crystal X-ray diffraction.DNBB crystallizes in a monoclinic system,space group P2 1/c with a=8.387(4),b=23.237(10),c=9.133(3),β=122.10(3)o,Z=4,V=1507.8(12) 3,D c=1.464 g/cm 3,F(000)=696.0,μ=0.116 mm-1,the final R=0.0480 and wR=0.1294.DNBB exhibited low toxicity on Caco-2 cell culture and produced significant inhibitory effect on the contraction of rat jejunal longitudinal smooth muscle (JLSM).The mechanism of DNBB on JLSM was correlated to the stimulation of α and β adrenergic receptors since α receptor antagonist phentolamine and β receptor antagonist propranolol abolished the inhibitory effects of DNBB on the contraction of JLSM,respectively.     

Synthesis,Crystal Structure and Bioactivity of a Pd(Ⅱ) Complex with Demethylcantharate and 2,2′-Bipyridine

A novel crystal with the molecular formula [Pd(DCA)(bipy)]2 [Pd(bipy)Cl2 ]·6.75H2O was formed by PdCl2 with disodium demethylcantharate (Na2 (DCA),DCA2= 7-oxa-bicyclo[2.2.1]heptane-2,3-bicarboxylate) and 2,2-bipyidine (bipy) through the hydrothermal method.The complex was characterized by elemental analysis and infrared spectroscopy.The structure of the complex was determined by single-crystal X-ray diffraction,which is of triclinic system,space group P1 with a=13.6818(7),b=14.8426(8),c=15.0043(8),α=97.319(3),β=92.521(3),γ=105.776(2)°,V=2898.4(3) 3,Dc=1.545 g·cm-3,Z=1,F(000)=1420,S=0.852,the final R=0.0525 and wR=0.1777 for 13634 observer reflections (I>2σ(I)).The binding reaction of the complex with ct-DNA and bovine serum albumin (BSA) was studied by fluorescence spectroscopy.The results indicated that the complex binds to ct-DNA via the partial intercalation.The binding constant K A of the complex interaction with BSA was 3.98×10 5 L·mol-1 and one binding site would be formed.The antiproliferative activity of the complex against human hepatoma cells (SMMC7721) in vitro is much higher than that of Na 2 (DCA).     

Synthesis,Crystal Structure and Biological Activity of N-（2,6-Difluorobenzoyl）-N＇-[5-（4-trifluoromethyl-phenyl）-1,3,4-thiadiazol-2-yl]ure

The title compound N-(2,6-difluorobenzoyl)-N'-[5-(4-trifluoromethylphenyl)-1,3,4-thiadiazol-2-yl]urea(C17H9F5N4O2S,Mr = 428.34) has been synthesized by the reaction of 2-amino-5-(4-trifluoromethylphenyl)-1,3,4-thiadiazole with 2,6-difluorobenzoyl isocyanate,and its crystal structure was determined by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P21/n with a = 10.7316(13),b = 10.5617(13),c = 16.037(2) ,β = 106.408(2)°,V = 1743.6(4) 3,Z = 4,Dc = 1.632 g/cm3,μ = 0.260 mm-1,F(000) = 864,the final R = 0.0599 and wR = 0.1420 for 3467 observed reflections with I > 2σ(I).The urea group,which adopts a planar configuration mediated by the intramolecular N-H...O hydrogen bond,is nearly coplanar with the thiadiazole and 4-trifluoromethylbenzene rings.The title compound was found to exhibit good fungicidal activity against Rhizoctonia solani and Botrytis cinerea.