Syntheses,Crystal Structures,and Antimicrobial Activities of 3-Bromo-N＇-（2- chloro-5-nitrobenzylidene）benzohydrazide and 3-Bromo-N＇-（4-nitrobenzylidene）benzohydrazide

Two new hydrazone compounds, 3-bromo-N'-(2-chloro-5-nitrobenzylidene)-ben- zohydrazide 1 and 3-bromo-N'-(4-nitrobenzylidene)benzohydrazide 2, have been synthesized and characterized by elemental analysis, IR spectra, 1H NMR, and single-crystal X-ray diffraction. Compound 1 crystallizes in monoclinic, space group P21/c with a=7.7924(10), b=24.490(3), c=7.8989(9) , β=94.987(6)°, V=1501.7(3) 3, Z=4, R=0.0345 and wR=0.0739. Compound 2 crystallizes in monoclinic, space group P21/c with a=7.4099(11), b=24.868(4), c=8.3255(12) , β=112.796(8)°, V=1414.3(4) 3, Z=4, R=0.0744 and wR=0.1912. Both compounds display E configurations with respect to the C=N double bonds. In the crystal structure of 1, molecules are linked through N-H…N and N-H…O hydrogen bonds, forming chains running along the c axis. In the crystal structure of 2, molecules are linked through N-H…O hydrogen bonds, forming chains running along the c axis. The preliminary antimicrobial activities were studied.     

A One-dimensional Metallic Oxide Constructed from Molybdenum Clusters and Mn（Ⅱ）-[3-（2-pyridyl） pyrazole] Cationic Coordination Components

A new polyoxomolybdate compound [Mn II (L) 2 (Mo 8 O 26) 0.5 ] 2n (1,L=3-(2-pyridyl)pyrazole) has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analyses,TG and IR spectroscopy.The compound crystallizes in the triclinic system,space group P1 with a=10.063(4),b=11.554(5),c=11.554(5),α=88.89,β=74.839(4),γ=74.839(4)o,V=1249.8(9) 3,C 16 H 14 MnMo 4 N 6 O 13,M r=937.03,D c=2.490 g/cm 3,μ(MoKα)=2.521 mm 1,F(000)=898,Z=2,the final R=0.0390 and wR=0.0970 for 4000 observed reflections (I > 2σ(Ⅰ)).Single-crystal X-ray diffraction analysis results reveal that compound 1 owns a chain structure based on β-[Mo 8 O 26 ] 4anions,which are linked by Mn II (L) 2 units via the terminal oxygen atoms.     

A Two-dimensional Metallic Oxide Constructed from Molybdenum Clusters and Ag（Ⅰ）-[3-（2-pyridyl）-pyrazole] Cationic Coordination Components

A new polyoxomolybdate compound [Ag 3 (HL) 4 ](PMo 12 O 40)] 1 (HL=3-(2-pyridyl)pyrazole) has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analyses,TG and IR spectroscopy.The compound crystallizes in triclinic,space group P1 with a=10.375(3),b=12.076(3),c=13.196(4),α=84.170(4),β=71.961(3),γ=86.326(4)°,V=1563.1(7)3,C 32 H 28 Ag 3 Mo 12 N 12 O 40 P,M r=2726.52,D c=2.897 g/cm 3,μ(MoKα)=3.366 mm 1,F(000)=1284,Z=1,the final R=0.0587 and wR=0.1312 for 4139 observed reflections (I > 2σ(Ⅰ)).X-ray diffraction analyses reveal that the PMo 12 O 40 3clusters in compound 1 are linked by four Ag 3 (HL) 4 3+ units via the terminal oxygen atoms to form a two-dimensional architecture.The symmetrical unit of Ag 3 (HL) 4 3+ exhibits two distinct Ag(Ⅰ) environments:a two-coordinate {AgN 2 } site and a five-coordinate {AgN 3 O 2 } site which links to two molybdate clusters.     

Synthesis,Structure,and Magnetic Property of One Novel Entangled Cobalt~Ⅱ-organic Compound

One novel entangled cobalt compound,{[Co 3 (nbta) 2 (4,4-bpy) 2 (H 2 O) 2 ](H 2 O) 2 } n (1,H 3 nbta=5-nitro-1,2,3-benzenetricarboxylic acid,4,4-bpy=4,4-bipyridyl),was prepared and characterized by X-ray diffraction,magnetism,elemental analysis,XPS,TGA and IR spectroscopy.The crystal of 1 crystallizes in monoclinic,space group Pc with a=13.0717(16),b=11.4167(14),c=15.9342(19),β=90.5190(10)o,V=2377.9(5)3,Z=2,C 48 H 36 Co 3 N 8 O 20,M r=1221.64,D c=1.706 g/cm 3,F(000)=1242 and μ(MoKα)=1.128 mm-1.The final R=0.0497 and wR=0.1461 for 4185 observed reflections with I > 2σ(I) and R=0.0721 and wR=0.1619 for all data.X-ray diffraction analyses revealed that Co(1) is linked by the nbta 3-ligands to form the ladder shape along the c axis,which is further extended into two-dimensional networks via the joint of Co(2) along the a axis.Moreover,these two dimensional motifs are interconnected by the 4,4-bpy bridges to form a complicated 3-D polymeric framework.Magnetic measurements revealed that compound 1 shows strong antiferromagnetic property.     

Syntheses and Crystal Structures of Two Octamolybdate Compounds Modified by CuⅡ-Imidazole Cations

Two new polyoxomolybdate compounds,namely(CuIIL2)2[CuⅡ(HL)2]2[Mo8O26(HL)2].(H2O)4(1) and [CuⅡ(HL)2]2[β-Mo8O26](HL)2(2)(HL=imidazole),were designed and synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that compound 1 consists of one Mo8O26(HL)24-cluster,two CuL2,two Cu(HL)22+,and four disassociated water molecules;and compound 2 is constructed by one β-Mo8O264-cluster,two Cu(HL)22+,and two uncoordinated imidazole molecules.     

Hydrothermal Syntheses and Structural Characterizations of Two ML-Containing Polyoxomolybdates:[Cu~Ⅱ_2(HL)_3]_2[Mo_8O_(26)]·(H_2O)_4 and [Ni~Ⅱ(HL)_3]_2(Mo_8O_(26))·(H_2O)_3(HL=3-(2-Pyridyl)pyrazole)

Two new polyoxomolybdate compounds,namely CuII2(HL)3]2[Mo8O26]·(H2O)4(1) and [NiII(HL)3]2(Mo8O26)·(H2O)3(2)(HL = 3-(2-pyridyl)pyrazole),were designed and synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that compound 1 consists of one β-Mo8O264-cluster and a Cu2 dimer which is built from two Cu(II) ions linked by three 3-(2-pyridyl)pyrazole ligands.Compound 2 is generated by two kinds of polyoxomolybdate clusters of α-[Mo8O26]4-and β-[Mo8O26]4-.In complexes 1 and 2,the multi-dimensional frameworks are con-structed with the help of hydrogen-bonding links between the terminaloxygen atoms of [Mo8O26]4-,water molecules,and 3-(2-pyridyl)pyrazole ligands.Crystal data of 1:C24H25Cu2Mo4N9O15,Mr = 1190.37,monoclinic,space group P21/c,a = 10.850(2),b = 18.510(4),c = 17.230(3) ,β = 100.57(3)°,V = 3401.6(12) 3,Z = 4,Dc = 2.324 g/cm3,F(000) = 2312,μ = 2.742 mm-1,R = 0.0302 and wR = 0.0775(Ⅰ 2σ(Ⅰ));Crystal data for 2:C48H48Mo8N18Ni2O29,Mr = 2225.98,monoclinic,space group P21/n,a = 20.799(2),b = 14.7970(13),c = 23.141(2) ,β = 91.6180(10)°,V = 7119.0(11) 3,Z = 4,Dc = 2.077 g/cm3,F(000) = 4344,μ = 1.968 mm-1,R = 0.0309 and wR = 0.0696(Ⅰ 2σ(Ⅰ)).     

Synthesis and Structural Characterization of a Polyoxomolybdate HNa_7[Mo_(36)O_(112)(H_2O)_(16)]·47H_2O

A new polyoxomolybdate complex HNa7[Mo36O112(H2O)16]·47H2O 1 has been prepared in the beaker solution and characterized by single-crystal X-ray diffraction and elemental analyses. Crystal data: H127Mo36Na7O175, Mr = 6542.79, monoclinic, C2/c, a = 40.891(6), b = 17.900(3), c = 25.580(4) , β = 125.673(2)°, V = 15210(4) 3, Z = 4, Dc = 2.857 g/cm3, F(000) = 12464, μ = 3.013 mm-1, R = 0.0633 and wR = 0.1654 (I > 2σ(I)). With the bridging sodium cations, the [Mo36O112(H2O)16]8- units in compound 1 are linked to form a one-dimensional structure, on the basis of which a three-dimensional architecture is further constructed via other sodium cations and complicated hydrogen bonds.     

Synthesis and characterization of a new open-framework zinc phosphite (4,4′-(C5H4N)2(CH2)3)·[Zn3(HPO3)4]

Employing 4,4-trimethylenedipyridine as a template,a new two-dimensional zinc phosphite (4,4-(C5H4N)2(CH2)3)· [Zn3(HPO3)4 ] has been prepared at room temperature and characterized by single-crystal X-ray diffraction,FTIR,elemental analysis,powder X-ray diffraction,and thermogravimetric analysis.The compound crystallizes in the monoclinic space group P2 1 /c,with cell parameters,a=9.3309(19),b=14.798(3),c=33.637(7),β=91.11(3),V=4643.8(16) nm 3 and Z=4.The connectivity of the ZnO4 tetrahedra and HPO 3 pseudo pyramids results in infinite corner-sharing 4-membered ring chains as second building units which are further linked by Zn O P bonds to form a 2-D layer that with interesting 8-membered ring channels along the [100] direction.The diprotonated 4,4-trimethylenedipyridine molecules sit in the middle of the layers along the [100] direction and interact with the framework via hydrogen bonds.     

Synthesis and Crystal Structure of a Polyoxomolybdate Framework Modified by Mn-L Units（L=3-（2-Pyridyl）pyrazole）

A new polyoxomolybdate compound,namely {[MnII(L)(4,4?-Hbipy)(H2O)2]2 [Mo5O15(PO4)2]}.2H2O 1(L = 3-(2-pyridyl)pyrazole,4,4'-Hbipy = protonated 4,4'-bipyridine),was designed and synthesized under hydrothermal conditions.Single-crystal X-ray diffraction analysis result reveals that the [Mo5O15(PO4)2]6-cluster in compound 1 links to two MnII cations via the oxygen of PO43-,which is further coordinated by one 3-(2-pyridyl)pyrazole,one 4,4'-Hbipyridine,and two water molecules.     

Two Zinc（Ⅱ） Carboxyarylphosphonates with Unusual Polynuclear Zn（Ⅱ） Units：Syntheses and Crystal Structures

[Zn2(PCP)(phen)(H2O)F]n 1 and {[Zn3(MCP)2(phen)2(H2O)]·2.5H2O}n 2(PCP = p-O2C(C6H4)PO33-,MCP = m-O2C(C6H4)PO33- and phen = phenanthroline) were obtained by hydrothermal synthesis and characterized by X-ray single-crystal diffraction.Compound 1 crystallizes in the monoclinic P21/c space group with a = 7.908(2),b = 20.254(3),c = 13.477(2) ,β = 107.76(3)°,V = 2055.7(8) 3,Z = 4,C20H16FN2O6PZn2,Mr = 561.10,Dc = 1.813 g/cm3,μ = 2.463 mm-1,F(000) = 1128,the final R = 0.0340 and wR = 0.0794.Compound 2 crystallizes in the monoclinic P21/n space group with a = 15.629(3),b = 18.141(4),c = 17.723(7) ,β = 121.89(2)°,V = 4267(2) 3,Z = 4,C40H31N4O13.5P2Zn3,Mr = 1041.70,Dc = 1.620 g/cm3,μ = 1.818 mm-1,F(000) = 2108,the final R = 0.0669 and wR = 0.1775.In compound 1,the tetranuclear Zn4 units are linked together by μ4-PCP3- to build 2D(4,4) layers,which are further interconnected through the μ2-bridging fluorion into a 3D framework with 1D phen ligands-filled channels.As for the 3D supramolecular framework of 2,the novel hexanuclear Zn6 units with "chair" conformation are extended by the moieties of μ4-MCP3- ligand to a 2D(4,4) layer on the bc plane,which is viewed as the 2-folded layers in 1.In both compounds,the structures are stabilized by hydrogen bonding interactions and π-π stacking interactions between the phen rings.Additionally,FT-IR spectroscopy and the fluorescent properties are discussed.     

Synthesis and Single-crystal Structure of a Silver(Ⅰ) Carboxyarylphosphonate: [Ag(H_2BCP)(4,4'-bipy)]·2H_2O

The title compound, a novel Ag(Ⅰ) carboxyarylphosphonate [Ag(H2BCP)(4,4'- bipy)]·2H2O (H3BCP = p-H2O3PCH2C6H4COOH, 4,4'-bipy = 4,4'-bipyridine), was synthesized by a hydrothermal reaction and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction. It belongs to monoclinic system, space group P21/c with a = 5.7038(11), b = 22.397(4), c = 5.602(4) ?, β = 106.26(3)°, V = 1913.4(7) 3, Z = 4, C18H20N2O7PAg, Mr = 515.20, Dc = 1.788 g/cm3, μ = 1.182 mm-1, F(000) = 1040, the final R = 0.0404 and wR = 0.1216 for 4178 observed reflections with I 2σ(Ⅰ). In the structure, the Ag(Ⅰ) cations are bridged by 4,4'-bipy to give rise to 1D chains running along the b axis. These chains are linked further by the interactions of O (from BCP ligands) and Ag atoms to yield 2D layers. Hydrogen bonding interactions and weak π-π stacking interactions between 4,4'-bipy rings assemble such adjacent layers to generate a 3D supramolecular architecture.     

Crystal Structure of a Ternary Copper(Ⅱ) Complex of N,N'-(p-Xylylene)dialanine Acid and 1,10-Phenanthroline

The compound [Cu2(bpy)2(PDIAla)(H2O)2](ClO4)2·H2O(H2PDIAla = N,N'-(p-xylylene)dialanine,bipy = 2,2'-bipyridine) 1 has been synthesized and structurally determined by single-crystal X-ray diffraction,elemental analyses and IR spectroscopy.The crystal belongs to the monoclinic system,space group P21 with a = 10.9772(6),b = 18.5464(9),c = 11.0790(6) ,β = 116.3110o,V = 2021.87(18) 3,Z = 2,Dc = 1.594 Mg/m3,Mr = 970.70,μ = 1.260 mm-1,F(000) = 996,λ(MoKα) = 0.71073 ,the final R = 0.0400 and wR = 0.1050 for all observed reflections.In the structure,the O(5)-H(52)···O(4) hydrogen bonding between aqua ligand and carbonyl oxygen of the H2PDIAla ligand along the c axis produce hydrogen-bonded helices which are assembled along the b axis through O(61)-H(61)···O(2) and N(6)-H(6N)···O(2) interactions to form 2-D layers that are further linked by π···π interactions between bpy ligands to yield a three-dimensional supramolecular network.     

Synthesis and Crystal Structure of（3S,4R,Z）-3,6-dimethyl-2-（3-methylbut-2-enylidene）-2,3,3a,4,7,7a-hexahydrobenzofuran-3,4-diol

The title compound of(3S,4R,Z)-3,6-dimethyl-2-(3-methylbut-2-enylidene)-2,3,3a,4,7,7a-hexahydrobenzofuran-3,4-diol,C15H22O3,as a potential gastric cytoprotective agent has been synthesized by the reduction of bisabolangelone in methanol with sodium borohydride.The title compound was characterized by IR and NMR spectra.Meanwhile,the crystal was obtained and determined by X-ray single-crystal diffraction.Crystal data:monoclinic system,space group P21 with a = 6.0692(12),b = 8.9954(18),c = 13.182(3) ,β = 92.59(3)°,V = 718.9(2) 3,Z = 2,F(000) = 272,Dc = 1.156 g/cm3,μ = 0.633 mm-1,R = 0.0362 and wR = 0.1051 for 9490 independent reflections(Rint = 0.0172) and 2461 observed reflections(I > 2σ(I)).Intermolecular O-H…O interactions link the molecules into one-dimensional infinite chains running along the b axis,which contributes to the stability of the crystal structure.     

An Orthorhombic Polymorph of Lanthanum Ultraphosphate LaP_5O_（14）：Synthesis, Structure and Density Functional Study

An orthorhombic polymorph of lanthanum ultraphosphate, LaP5O14, was firstly synthesized by the high temperature solid-state reaction and structurally characterized by single-crystal X-ray diffraction technique. It crystallizes in the orthorhombic Pmna space group with a=13.155(3), b=8.816(2), c=9.115(2) , V=1057.1(4) 3 and Z=4. The structure features (P5O14)3-anionic ribbons linked with neighboring LaO8 polyhedra. The title solid-state compound is an insulator. Theoretically calculated energy band structure, density of states (DOS), and optical response function by density function theory (DFT) for LaP5O14 were also performed.     

A New Cadmium（Ш） Polymer Based on 3,5-Pyrazoledicarboxylic Acid：Hydrothermal Synthesis and Crystal Structure

The reaction of CdCl3.2.5H2O with 3,5-pyrazoledicaiboxylic acid under hydrother-mal conditions produce a novel three-dimensional(3-D) coordination polymer [Cd2(C5H2O4N2)2.2H2O]n.The title compound crystallizes in the monoclinic system,space group P21/c with a = 6.422(4),b = 12.334(7),c = 8.936(6) ,β = 104.793(7)°,V = 684.4(7) 3,Z = 4,Dc = 2.761 g/cm3,μ = 3.181 mm-1,F(000) = 544,R = 0.0248 and wR = 0.0624.In the crystal structure of the title compround,molecules are linked through N-H...O hydrogen bonds,forming chains running along the a axis.Every Cd(Ш) coordinates with four molecules of ligand and one water molecule,forming a pentagomal-bipyramidal geometry.     

Synthesis and Characterization of （4R,5R）-1,3-dioxolance-4,5-bis（2-pyridineacrboxylic acid）

The title compound, (4R,5R)-1,3-dioxolance-4,5-bis(2-pyridineacrboxylic acid), has been synthesized and characterized by single-crystal X-ray diffraction, IR, NMR, and MS analyses. Crystal structure of the title compound was grown from ETOH by slow diffusion at room temperature. The title compound crystallizes in monoclinic, space group C2 with a = 17.805(3), b = 11.459(3), c = 11.1656(17) , β = 113.066(4)°, V = 2095.9(6) 3, Z = 4, F(000) = 880, Dc = 1.332 Mg/m-3, C23H20N2O6, Mr = 420.41 and μ = 0.10 mm-1     

Synthesis,Crystal Structure,and Antitumor Activity of 1-（4-Methoxybenzylidene）-2-（1-phenyl-6-trifluoromethyl- 1H-pyrazolo [3,4-d] pyrimidin-4-yl）hydrazine Monohydrate

The novel title compound 1-(4-methoxybenzylidene)-2-(1-phenyl-6-trifluoromethyl-1H-pyrazolo[3,4-d]pyrimidin-4-yl)hydrazine monohydrate(C20H15F3N6O·H2O, Mr = 430.40) has been synthesized by a four-step procedure including the cyclization, chlorination, hydrazinolysis and condensation reaction, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to orthorhombic, space group Pbca with a = 8.3779(13), b = 17.607(3), c = 26.774(4) , V = 3949.2(11) 3, Z = 8, Dc = 1.448 g/cm3, μ = 0.117 mm–1, F(000) = 1776, the final R = 0.0553 and wR = 0.1516 for 2354 observed reflections with I 2■(I). X-ray diffraction analysis reveals that the title compound is almost coplanar except for the trifluoromethyl and phenyl moieties. In the crystal packing, the molecules are linked by intermolecular O(1W)–H(1WA)···N(2), O(1W)–H(1WA)···N(4) and N(5)–H(5A)···O(1W) hydrogen bonds via water molecules and stacked through π-π stacking interactions. The preliminary bioassay suggested that the title compound exhibits relatively good antitumor activity against HepG2 and BCG-823.     

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).     

Synthesis,Crystal Structure and Theoretical Calculation of 1,1＇,5,5＇-Tetramethyl-2,2＇-diphenyl-4,4＇-[i-phenylene-bis（methylidy-nenitrilo）]di-1H-pyrazol-3（2H）-one

1,1',5,5'-Tetramethyl-2,2'-diphenyl-4,4'-[i-phenylenebis(methylidynenitrilo)]di-1H-pyrazol-3(2H)-one was synthesized and characterized by X-ray single-crystal diffraction analysis.The crystal crystallizes in monoclinic,space group P21/c with a = 6.1375(1),b = 24.6571(4),c = 17.7487(3) ,β = 94.781(1)°,V = 2676.62(8) 3,C30H28N6O2,Mr = 504.58,Z = 4,Dc = 1.252 g/cm3,F(000) = 1064,μ = 0.081 mm-1,R = 0.0463 and wR = 0.1153(I > 2σ(I)).Theoretical studies of the title compound were carried out by density functional theory(DFT) BLYP method,using ADF program package.It indicates that N(26) and N(41) are active sites of the title compound.     

Synthesis and Crystal Structure of 4-[（1E）-（4-Hydroxy-3,5-dimethoxybenzylidene）-amino]-1,5-dimethyl-2-phenyl-2,3-dihydro-1H-pyrazol-3-one

The title compound (C20H21N3O4, Mr = 367.40) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal is of orthorhombic, space group P212121 with a = 7.5143(15), b = 13.901(3), c = 18.545(4) , V = 1937.1(7) 3, Z = 4, Dc = 1.260 g/cm3, μ = 0.089 mm-1, F(000) = 776, the final R = 0.0616 and wR = 0.0912. X-ray diffraction reveals that the molecule adopts an E configuration about the central C=N double bond. The intermolecular O–H…O hydrogen bond stabilizes the crystal structure by causing the formation of a supramolecular architecture.