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

A new polyoxomolybdate compound [Zn(HL)2(Mo8O26)(4,4'-Bipy)]·(4,4'-Bipy) (HL = 3-(2-pyridyl)pyrazole, 4,4'-Bipy = 4,4'-bipyridine) 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses, TG and IR spectroscopy. The compound crystallizes in monoclinic, space group C2/c with a = 18.060(4), b = 13.870(3), c = 19.360(4) , β = 93.50(3)°, V = 4840.5(17) 3, C36H30Mo8N10O26Zn, Mr = 1851.59, Dc = 2.541 g/cm3, μ(MoKα) = 2.589 mm·1, F(000) = 3560, Z = 4, the final R = 0.0328 and wR = 0.0870 for 4005 observed reflections (I > 2σ(I)). X-ray diffraction analyses reveal that compound 1 is constructed from Mo8O264-units linked by Zn(HL)22+ and 4,4'-Bipy. Mo8O264-is connected by Zn(HL)22+ via terminal oxygen atoms along the [010] axis forming chains, which are further linked by 4,4'-Bipy along the [001] axis forming a two-dimensional network structure.     

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.     

Hydrothermal Synthesis and Structural Characterization of a Novel Organic—Inorganic Hybrid Compound {[Cu（2,2′—bpy）2]2—Mo8O26}

A novel organic-inorganic hybrid compound {[Cu(2,2′-bpy)2]2Mo8O26} has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction. The compound crystallizes in the orthorhombic space group, Pna21,with a=2.4164(5),b=1.8281(4),c=1.1877(2)nm,V=5.247(2)nm^3,Z=4,and final R1=0.0331,wR2=0.0727.The structure consists of discrete {[Cu(2,2′-bpy)2]2Mo8O26} clusters,constructed from a β-octamolybdate subunit[Mo8O26]^4- covalently bonded to two [Cu(2,2′-bpy)2]^2 coordination complex cations via bridging oxo groups.In addition,the spectroscopic properties and thernal behavior of this compound have been investigated by spectroscopic techniques (UV-vis,IR,Raman and EPR spectra) and TG analysis.     

A One-dimensional Manganese(Ⅱ) Coordination Polymer with 4'-Hydroxybiphenyl-4-carboxylate as the Single Ligand:Synthesis,Crystal Structure and Luminescence

A new 1D coordination polymer,{[Mn2(4',4-hbc)4(4',4-Hhbc)2(H2O)]·H2O}n(4',4-Hhbc=4'-hydroxyl-biphenyl-4-carboxylic acid),has been hydrothermally synthesized and struc-turally characterized by elemental analysis,IR spectroscopy and single-crystal X-ray diffraction.The crystal belongs to the monoclinic system,space group C2/c with a=52.421(10),b=7.5388(15),c=16.478(3),β=106.12(3)°,V=6256(2)3,Z=4,C78H62Mn2O21,Mr=1445.16,Dc=1.534g/cm3,μ(MoKα)=0.490mm-1,F(000)=2992,R=0.0764 and wR=0.2006 for 2984 observed reflections with I2σ(I).X-ray diffraction analyses reveal that the title compound is a one-dimensional infinite chain,in which the MnⅡ atom adopts a distorted octahedral geometry coordinated by four 4',4-hbc ligands,one 4',4-Hhbc ligand and one water molecule.Furthermore,the luminescent property of title compound was investigated.     

Structure and Luminescence Property of a Hexanuclear Thiosemicarbazone Silver（I） Cluster

A new hexanuclear silver(I) compound containing thiosemicarbazones with groups of 1-naphthalene was synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analysis and fluorescence spectrum.The title compound crystallizes in monoclinic,space group P2 1 /c with a=16.101(4),b=24.855(7),c=14.492(4),β=109.730(5)°,V=5459(3)3,C 90 H 102 Ag 6 N 24 O 6 S 6,M r=2455.54,D c=1.494 g/cm 3,μ(MoKα)=1.228 mm-1,F(000)=2472,Z=2,the final R=0.0761 and wR=0.1507 for 5258 observed reflections (I > 2σ(I)).In the structure,the S atom of ligand L serves as a triply bridged chelator to connect the six silver atoms into a Ag 6 L 6 cluster.Luminescence investigation reveals that the compound exhibits two ligand-independent cluster-centered electron transfer bands and one ligand-dependent charge transfer band.     

Synthesis and Crystal Structure of a New Two-dimensional Manganese Coordination Polymer： [Mn（L）（1,4-bdc）]

A new coordination polymer,[Mn(L)(1,4-bdc)] (L=11-fluoro-dipyrido[3,2-a:2,3-c]phenazine,1,4-bdc=benzene-1,4-dicarboxylate),has been synthesized through the hydrothermal method and characterized by elemental analysis,IR and single-crystal X-ray diffraction.It crystalli-zes in triclinic,space group P1 with a=9.7544(9),b=10.8254(10),c=11.5288(10),α=114.1300(10),β=96.6110(10),γ=105.0390(10)°,V=1038.62(16)3,Z=2,C 26 H 13 FMnN 4 O 4,M r=519.34,D c=1.661 g/cm 3,F(000)=526,μ(MoKa)=0.691 mm-1,R=0.0405 and wR=0.0977.The 1,4-bdc dianions link the neighboring Mn(II) atoms to yield a two-dimensional layer structure.The L ligands are attached on both sides of the layer.The π-π interactions between the L ligands of neighboring layers result in a three-dimensional supramolecular architecture.     

Synthesis and Crystal Structure of 2,6-Bis（2-pyridinylmethyl）-3,5-bis（2-hydroxyl-5-chlorophenyl）pyrazine

The title compound,2,6-bis(2-pyridinylmethyl)-3,5-bis(2-hydroxyl-5-chlorophe nyl)-pyrazine(C26H12Cl2N4O2C2H8O2,Mr=551.41),has been synthesized and characterized by LC-ESIMS,NMR,UV and IR spectroscopy as well as by X-ray single-crystal diffraction.The compound behaves as a substituted pyrazine.The hydrogen atoms on C(2) and C(3) are substituted by 2-pyridinyl,whereas those on C(1) and C(4) are substituted by 2-hydroxyl-5-chlorophenyl.It crystallizes in the monoclinic system,space group P21/c with a=8.9433(12),b=32.003(4),c=10.5209(18),β=111.199(2)°,V=2807.5(7)3,Z=4,Dc=1.305 mg/m3,F(000)=1144 and μ=0.094 mm-1.A total of 13235 reflections were collected in the range of 2.17～25.01o by using a phi and omega scan mode,of which 4923 were unique(Rint=0.0692) and 2872 observed reflections with Ⅰ > 2σ(Ⅰ) were used in the structure solution and refinement.     

A New Supramolecular Compound Based on Cd（II）-Schiff-base and Keggin-type [PMo_（12）O_（40）]~3

A new supramolecular compound, {[Cd(L)2]2[PMo12O40NO3]·CH3CN·2H2O}n 1 (L is 1,4-bis(4-imidazolyl)-2,3-diaza-1,3-butadiene), based on Cd(II)-Schiff-base and Keggin- type [PMo12O40]3- was synthesized via self-assembly and structurally characterized by elemental analysis, infrared spectroscopy, and single-crystal X-ray diffraction analysis. The crystal is of triclinic, space group P1 with a = 12.0128(11), b = 13.6196(13), c = 13.9995(13) , α = 103.868(2), β = 95.225(2), γ = 101.024(2)°, V = 2160.0(3) 3, Z = 1, C34H39N26O45Cd2Mo12P, Mr = 2938.96, Dc = 2.259 g/cm3, μ = 2.276 mm-1, F(000) = 1400, the final R = 0.0565 and wR = 0.1613 for 4973 observed reflections with I 2σ(I). The crystal structure can be described by the packing of Keggin anionic and Metal-Schiff-base cationic layers.     

Synthesis and Crystal Structure of 1,2-Bis-（p-nitrophenylsulfonamido）-4,5-dinitrobenzene

The title compound, 1,2-bis-(p-nitro-phenylsulfonamido)-4,5-dinitrobenzene, was synthesized and characterized by elemental analysis, IR and 1H NMR. A pale yellow prism crystal of C23H26N8O13S2 (Mr = 686.64) was obtained in DMF solution and determined by single-crystal X-ray diffraction method. It crystallizes in triclinic system, space group P1 with a = 10.346(4), b = 12.210(5), c = 12.976(5) , α = 108.220(8), β = 99.482(4), γ = 95.490(4)°, V = 1516.7(10) 3, Z = 2, Dc = 1.504 g/cm3, F(000) = 712, μ = 0.254, Mr = 686.64, the final R = 0.0561 and wR = 0.1487. One sulfonamido group of the title compound is deprotoned and forms N(3)=C(13). The crystal involves N,N-dimethylamine from the decomposition of DMF and the proton is transferred to N,N- dimethylamine. It is a strong proof for the characterization of deprotoned recognition compound by X-ray single-crystal structure.     

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.     

Synthesis,Crystal Structure and Biological Activity of 8-（（4-（（2,3-diaminopyridin-4-yl）oxy）-3-fluorophenyl）-amino）-2-（4-fluorophenyl）-3-methyl-2,7-naphthyridin-1（2H）-one

The new title compound 8-((4-((2,3-diaminopyridin-4-yl)-oxy)-3-fluorophenyl)-amino)-2-(4-fluorophenyl)-3-methyl-2,7-naphthyridin-1(2H)-one(C26H20F2N6O2, Mr = 486.48) has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic, space group P21/c with a = 15.365(3), b = 13.144(2), c = 11.863(2), β= 108.882(3)°, Z = 4, V = 2267.0(7)3, Dc = 1.425 g/cm3, F(000) = 1008, μ = 0.105 mm-1, MoKa radiation(λ = 0.71073), R = 0.0480 and wR = 0.1294 for 3197 observed reflections with I 2σ(I). X-ray diffraction analysis reveals that the region C(substituents of 8-amino group and 3-methyl group on the 2,7-naphthyridin-1(2H)-one ring) of compound 6 are effectively planar. Intramolecular and intermolecular hydrogen bonds together with π···π interations are found in the structure. In addition, compound 6 shows potent c-Met and c-Kit kinase inhibition activities.     

Synthesis, Crystal Structure and Luminescence Property of a 2D Mn（II） Coordination Polymer Based on Isoniazid

A novel 2D Mn(Ⅱ) coordination polymer [Mn(CH3COO)2(INH)]n(INH=isoniazid) has been synthesized in DMF solution with isoniazid and Mn(CH3COO)2 . The polymer was characterized by single-crystal X-ray diffraction analysis, FTIR and X-ray powder diffraction (XRPD). The crystal belongs to the monoclinic system, space group P2 1 /c with a=9.3251(18), b=16.340(3), c=8.8096(17) , β=94.747(3)°, V=1337.7(4) 3 , Z=4, μ(MoKα)=1.006 mm -1 , F(000)=636, R=0.0754 and wR=0.1375 (I > 2σ(I)). In the complex, each Mn(Ⅱ) atom is coordinated to three CH3COO- groups and two INH ligands. The Mn(Ⅱ) atoms locate in a distorted coordination octahedron and are bridged by CH3COO- ions to form a 1D S shaped chain extending along the c direction. The INH molecules act as bridges to link the Mn(Ⅱ) atoms of adjacent chains and further construct a lamellar polymer. The remaining coordination site is occupied by an O atom of the other CH3COO-. The experimental results show that the title complex has good luminescence property and could be used as potential optical materials.     

Synthesis and Crystal Structure of a New Supramolecular Compound Constructed from Flexible 1,1＇-（1,4-Butanediyl）bis（imidazole） and 1,2,4,5-Benzenetetracarboxylic Acid

A new bis(imidazolium) compound,[H2L(H2btec)2]·H4btec(1,L=1,1'-(butane-1,4-diyl)bis(imidazole),H4btec=1,2,4,5-benzenetetracarboxylatic acid),has been synthesized and structurally characterized by single-crystal X-ray diffraction.The title compound crystallizes in the monoclinic system,space group Pnma,with a=13.3908(11),b=13.9249(12),c=16.2166(14),V=2957.6(4)3,Z=4,Mr=698.55,Dc=1.569 mg/m3,F(000)=1448,μ(MoKα)=0.130 mm-1,the final R=0.0584 and wR=0.1538 for 4295 observed reflections with I2σ(I).The compound consists of one 1,1'-(butane-1,4-diyl)bis(imidazolium) cation,one neutral H4btec and one H2btec2-(Only two para carboxyl groups are deprotonated,and two protonated ones remain free) anion.A one-dimensional hydrogen bonding chain and a 2D hydrogen bonding network are formed via intermolecular N-H…O and O-H…O hydrogen bonds.These adjacent chains are further stacked through intermolecular π-π and hydrogen bonding interactions to form a 3D supramolecular network.     

A New 3D Supramolecular Network Formed by [Zn_3（2,6-Pyridinedicarboxylate）_3Cl_4]~（4-）and 4-Carboxypyridinium

A new compound [Zn3(C7NO4H3)3Cl4]·[C6NO2H6]4·4H2O (I) has been synthesized and structurally characterized by X-ray crystallography.It crystallizes in monoclinic,space group C2/c with a=16.9018(14),b=12.6902(10),c=25.1170(2),β=90.54°,V=5387.0(8)3,Z=4,Zn3C45H41Cl4N7O24,Mr=1401.76,Dc=1.728 g/cm3,F(000)=2840,μ(MoKa)=1.615 mm-1,the R= 0.0758 and wR=0.2060 for 3468 observed reflections (I 2σ(I)).Analysis of single-crystal X-ray diffraction data shows that compound I displays an interesting example of 3D supramolecular networks with perfect neutral and ionic hydrogen bonding array.     

S-（＋）-（E）-1-（2-furfuryl）-5-substituted-1,3,5-hexahydrotriazine-2-N-nitroimines：Synthesis,Crystal Structure and DFT Calculations

A novel neonicotinoid analogue(C13H19N5O5,3a)had been synthesized,the structure was characterized by elemental analysis,IR and 1H NMR spectra,and the S-(+)-(E)-configuration was confirmed by single-crystal X-ray diffraction.The crystal belongs to monoclinic,space group P21 with a = 8.7076(17),b = 8.3211(17),c = 10.642(2),β = 92.370(3)o,V = 770.4(3)3,Z = 2,Dc = 1.402 g/cm3,μ = 0.110 mm-1,Mr = 325.33,F(000)= 344,S = 1.027,R = 0.0543 and wR = 0.1229 for 3601 unique reflections with 2919 observed ones(I > 2σ(I)).Compound 3a is stabilized by intramolecular hydrogen bonds and intermolecular force.In addition,the structure of compound 3a was optimized by the B3LYP/6-31G(d,p).DFT/B3LYP optimizations were performed based on X-ray geometries applying 6-31G(d,p)basis set.The optimized structure of compound 3a by the B3LYP/6-31G(d,p)method is more bent than in the crystal.IR spectrum of the solid compound is consistent with the X-ray structure.The HOMO-LUMO gap in 3a(5.3 eV)indicates high kinetic stabilities of compound 3a.The preliminary bioassay test showed that 3a exhibited good activities against Nilaparvata legen,Pseudaletia separate Walker and Aphis medicagini at 500 mg/L.     

Hydrothermal Synthesis and Crystal Structure of a 2D Zinc（Ⅱ） Coordination Polymer with 5-Hydroxynicotinic Acid

The title compound,[Zn(5-hydroxynicotinate) 2 2H 2 O] n,has been synthesized by reacting zinc sulfate vitriol with 5-hydroxynicotinic acid under hydrothermal conditions,and its structure was determined by X-ray crystallography with the following data:monoclinic,space group C2/c,C 12 H 12 N 2 O 8 Zn,M r=377.61,a=10.223(3),b=10.319(3),c=13.613(4),β=105.922(6)°,Z=4,V=1380.9(8)3,F(000)=768,D c=1.816 g/cm 3,μ(MoKα)=1.826 mm-1,the final R=0.0401 and wR=0.1380 for 1157 observed reflections (I > 2σ(I)).In the structure of the title compound,the Zn II ion located in an inversion center lies in a distorted tetrahedral environment at a N 2 O 2 coordination mode,and the 5-hydroxynicotinic acid ligand links symmetry-related Zn II ions at a μ 2-N,O bridging way forming a two-dimensional covalent structure.In the crystal,solvent water molecules form intermolecular O-H O hydrogen bonds and pyridine rings of adjacent layers form π-π stacking (3.346),which connect adjacent two-dimensional sheets into a three-dimensional supramolecular network.     

Synthesis,Spectroscopic Properties and Crystal Structure of 3,3＇-（Anthracene-9,10-diyl）bis（1-phenylpropan-1-one）

The compound 3,3'-(anthracene-9,10-diyl)bis(1-phenylpropan-1-one)(C32H26O2,Mr=442.55) has been synthesized by the reaction of 2,2'-(anthracene-9,10-diylbis(methy-lene))bis(1,3-diphenylpropane-1,3-dione) with CsCO3,and its structure was characterized by 1H NMR and single-crystal X-ray diffraction.The crystal of the title compound belongs to monoclinic,space group P21/c with a=9.154(3),b=5.2777(16),c=24.897(7) nm,β=107.337(10)°,Z=2 and V=1.1482 nm3.X-ray analysis indicates that an intermolecular hydrogen bond C(8)-H(8A)…O(1),weak C-H···π between H(9A) and the centre of anthracene rings and weak π-π interactions between two anthracene ring planes are observed.     

Layer Zirconogermanate——(H_2DETA)[ZrGe_3O_8F_2] Showing Odd 3MR and 7MR

A layered zirconogermanate,(H2DETA)[ZrGe3O8F2](1),was hydro(solvo)thermally synthesized with diethylenetriamine(DETA) as template,and structurally determined by X-ray single-crystal diffraction. Compound 1 crystallized in the monoclinic space group P21/c with data of unit cell:a=0.7644(2) nm,b=1.1235(2) nm,c=1.6860(3) nm,V=1.4479(5) nm3,μ(Mo Kα)=6.931 mm-1,Z=4,R1=0.0402 for 3236 reflections with Fo>2σ(Fo). The structure of compound 1 was formed by alternatively packing the inorganic layer of ZrGe3O8F2 and H...     

Synthesis and Crystal Structure of a Heterometallic Chain Coordination Polymer:{[Ni_2Mn_2L_2(CH_3CH_2OH)(H_2O)]·CH_3OH·2H_2O}_n

A chain-like coordination polymer with the chemical formula of {[Ni2Mn2L2(CH3CH2OH)-(H2O)]·CH3OH·2H2O}n has been synthesized by the assembly reaction of K2NiL·H2O and Mn(OAC)2·4H2O with a 1:1 mole ratio in methanol,where OAC-=CH3COO-and H4L=2-hydroxy-3-[(E)-({2-[(2-hydroxybenzoyl)imino]ethyl}imino)methyl]benzoic acid.The crystal structure was determined by single-crystal X-ray diffraction analysis.It belongs to the triclinic system,space group P1,with a=9.9464(8),b=13.4718(11),c=14.3877(12),α=87.1930(10),β=85.4280(10),γ=74.6470(10)°,V=1852.4(3)3,Z=2,Dc=1.807g/cm3,Mr=1008.03,λ(MoKα)=0.71073,μ(MoKα)=1.794 mm-1,F(000)=1032,R=0.0527 and wR=0.1284(Ⅰ2σ(Ⅰ)).The compound exhibits a chain-like structure formed by dissymmetrical tetranuclear units.     

Synthesis and Crystal Structure of 2-（1-Naphthalenylamino）-4-thiazolidinone

The compound 2-(1-naphthalenylamino)-4-thiazolidinone was synthesized by the reaction of 1-(naphthalene-1-yl)thiourea with ethyl chloroacetate in an ionic liquid, and its structure was characterized by IR, 1H NMR and single-crystal X-ray diffraction. The crystal of the title compound belongs to monoclinic, space group P21 /c with a=10.0081(3), b=14.5312(4), c=7.8739(2) , β=99.425(3)°, Z=4, V=1129.64(5)3 , Dc=1.425 g/cm3 , μ=0.269 mm-1 , F(000)=504, the final R=0.0519 and wR=0.1507. X-ray analysis indicated that the five-membered ring is essentially planar in this molecule, and intermolecular hydrogen bonds N(1)-H(1)…N(2), C(3)-H(3)…O(1), C(4)-H(4)…O(1) and C(12)-H(12a)…O(1) were observed. π-π Stacking interactions contribute to the stability of the structure. DSC-TG analysis showed that the title compound experienced a phase change at 190 ℃ and began to decompose above 240 ℃.