层状K4Ag2Sn3S9·2H2O的溶剂热合成与表征

用溶剂热法合成了K4Ag2Sn3S9·2H2O,通过单晶X射线衍射、DSC、TG、IR和紫外漫反射光谱等手段对其进行了表征.结果表明,K4Ag2Sn3S9·2H2O属单斜晶系,P21/m空间群,a=0.78071(2)nm,b=2.73508(1)nm,c=1.05008nm,α=90°,β=103.87(6)°,γ=90°,Z=4.其层状结构内具有一维孔道,钾离子分离在层间及层内孔道中.     

Hydrothermal Synthesis and Crystal Structure of a Cobalt(Ⅱ) Coordination Polymer: [Co(C2O4)(bix)]n (bix=1,4-Bis(imidazol-1-ylmethyl)-benzene)

<正>A new two-dimensional cobalt coordination polymer has been prepared and fully characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. The compound [Co(C_2O_4)(bix)]_n 1 crystallizes in the monoclinic system, space group C2/c, with a = 11.549(3), b = 15.700(3), c = 9.260(2), β = 102.984(3)°, V = 1636.0(6)~3, C_(16)H_(14)CoN_4O_4, M_r = 383.23, D_c = 1.556 g/cm~3, μ(MoKα) = 1.078 mm~(-1), F(000) = 780, Z = 4, the final R = 0.0455 and wR = 0.1286 for 1483 observed reflections (I > 2σ(I)). Of the compound, the Co center is octahedrally coordinated with oxalate acting as a tetra-dentate ligand coordinated to the cobalt atom and each bix serving as a bridging ligand by employing two N-donors to coordinate with the Co center. An infinite {Co_2(C_2O_4)_2}_∞ chain is formed along the a axis. Furthermore, the 1D chains are held together via bix ligands to generate a two-dimensional network structure with 1D coronal-like channels (ca. 5.691 × 15.700).     

Synthesis, Crystal Structure and Band Structure of EuMg6Sn3.67

EuMg6Sn3.67 has been synthesized by reacting the mixture of the corresponding pure elements at high temperature, and structurally characterized by single-crystal X-ray diffraction study. EuMg6Sn3.67 crystallizes in hexagonal space group P63/m (No. 176) with a = 11.7259(4), c = 4.5507(2), V = 541.88(4)3 , Z = 2, Mr = 734.60, Dc = 4.502 g/cm3 , μ = 14.348 mm-1 , F(000) = 638, the final R = 0.0128 and wR = 0.0378 for 464 observed reflections with Ⅰ > 2σ(Ⅰ). EuMg6Sn3.67 is closely related to the Ba2Mg12Ge7.33 structure type and features a three-dimensional Mg6Sn3.67 framework with one-dimensional hexagonal tunnels along the c-axis occupied by the Eu atoms. Electronic structure calculation indicates that the title compound is metallic.     

Ba5Ga4Se10: a new selenidogallate containing the novel [Ga4Se10](10-) anionic cluster with Ga in a mixed-valence state

The new compound Ba(5)Ga(4)Se(10) has been synthesized for the first time. It crystallizes in the tetragonal space group I4/mcm with a = 8.752(2) ?, c = 13.971(9) ?, and Z = 2. The structure contains discrete [Ga(4)Se(10)](10-) anions and charge-compensating Ba(2+) cations. The novel highly anionic [Ga(4)Se(10)](10-) cluster is composed of two Ga(Se)(4) tetrahedra and two Ga(Ga)(Se)(3) tetrahedra with Ga in the 2+/3+ valence states. It also exhibits an unusually long Ga-Se distance of 2.705(2) ?, which has only been observed under high pressure conditions before. A band gap of 2.20(2) eV was deduced from the UV/vis diffuse reflectance spectrum.     

Synthesis,Crystal and Electronic Structure of Ba_3ZnSb_2O_9 with the 6H-perovskite-type Structure

Crystals of Ba3ZnSb2O9 have been grown by a high-temperature solid-state reaction and characterized by single-crystal X-ray diffraction.Ba3ZnSb2O9 crystallizes in the hexagonal P63/mmc space group with a = 5.8663(4),c = 14.478(2) ,V = 431.49(8) 3,Z = 2 and R(all data) = 0.0167.The structure of Ba3ZnSb2O9 consists of pairs of face-sharing Sb2O9 bi-octahedra connected via corners with two single layers of mutually isolated ZnO6 octahedra.Each Ba2+ ion is bonded to 12 oxygen atoms.The UV-vis absorption spectrum of the compound has been investigated.Additionally,the calculations of band structure and density of states have also been performed with density functional theory method.The obtained results tend to support the experimental data of the absorption spectrum.     

Synthesis and Crystal Structure of a Luminescent Compound 5-（1H-benzoimidazol-2-yl）- 3H-[ 1,2,3 ] triazole-4-carboxylic Acid

The title compound, 5-(1H-benzoimidazol-2-yl)-3H-[1,2,3]triazole-4-carboxylic acid (C10H7N5O2·C3H7NO, Mr=302.30), has been synthesized and characterized by FT-IR and ESI-MS, 1 H-NMR spectroscopy and X-ray single-crystal diffraction. Crystal structure of the title compound was grown from DMF by slow diffusion at room temperature. Crystal data: orthorhombic structure, space group Pna21 with a=6.9635(3), b=19.4398(7), c=30.6165(12), V=4144.5(3)3, Z=12, Dc=1.454 g/cm 3, μ(MoKα)=0.108 mm-1, and F(000)=1896. The structure was refined to R=0.0450 and wR=0.0975 for 3578 observed reflections with I>2σ(I). The intermolecular hydrogen bonds and π-π stacking further stabilize the structure.     

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.     

Synthesis and Crystal Structure of a New Mixed-ligand Nickel（Ⅱ） Coordination Polymer： [Ni（L）（cis-1,4-chdc）]n·1.25nH2O

A new one-dimensional Ni(II) coordination polymer [Ni(L)(cis-1,4- chdc)]n?1.25nH2O has been synthesized under hydrothermal conditions by using 1,4-cyclohexanedicarboxylic acid (1,4-H2chdc) and 2-(3-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline (L). Crystallographic data for the compound: triclinic, space group P with a=8.777(2), b=10.662(2), c=13.799(3), α=89.480(4), β=73.933(3), γ=81.980(4)°, V=1228.2(5)3, Z=2, C27H22.50FN4NiO5.25, Mr=568.70, Dc=1.527 g/cm3, F(000)=583, μ(MoKa)=0.846 mm-1, R=0.0634 and wR=0.1465. Neighboring Ni(II) atoms are linked by the cis-1,4-chdc ligands to generate a one-dimensional chain structure. The π-π interactions between the L ligands of neighboring chains led to the formation of a two-dimensional supramolecular layer. The elemental analysis, IR spectrum and TG of the compound have been studied.     

Synthesis and Crystal Structure of a Ruthenium（Ⅱ） Compound of Dinitrogen

The title compound [Ru（bph）（PPh3）2（N2）]·（PF6）·1.5CH2Cl2 （bph = N-（benzoyl）- N＇-（picolinylidene）-hydrazine） has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group P21/n with a = 13.5201（6）, b = 15.5078（6）, c = 25.0656（13） A, β= 100.257（3）°, C50.50H43Cl3F6N5OP3Ru, Mr= 1150.23, V= 5171.4（4） A3, Z = 4, F（000） = 2332, Dc = 1.477 g/cm^3 and ,μ（MoKa） = 0.615 mm^-1. The structure was refined to R = 0.0524 and wR = 0.1398 for 8060 observed reflections （I 〉 2σ（I））. The Ru-N2 and N-N bond distances are 1.919（4） and 1.133（5）A, respectively.     

A New Chain-like Copper（Ⅱ） Polymer： [Cu（MOPIP）（BDC）]n·0.5n（H2O）

A metal-organic coordination compound formulated as [Cu（MOPIP）（BDC）]n·0.5n（H2O） 1 （MOPIP - 2-（4-methoxyphenyl）-1H-imidazo[4,5-f][1,10] phenanthroline, BDC = 1,4-benze Nedicarboxylate） has been hydrothermally synthesized and structurally characterized by elemental analysis, thermogravimetric analysis, IR spectrum, and single-crystal X-ray diffraction. The title compound crystallizes in the triclinic system, space group P1^-, with a = 8.872（5）, b = 11.163（6）, c = 12.589（6）A, α = 94.687（7）, β = 99.930（6）, γ = 103.074（7）°, V = 1186.7（12）A^3, C28H19CuN4O5.5, Mr= 563.01, Dc = 1.576 g/cm^3,μ（MoKa） = 0.973 mm^-1, F（000） = 576, Z = 2, the final R = 0.0607 and wR = 0.1618 for 3419 observed reflections （I 〉 2σ（I））.     

Synthesis and Crystal Structure of Chiral Spiro{1-bromo-4-hydroxy-5-N-cyclohexyl-butyrolactam-6-oxo-dirings[3.1.0]hexane-2,3′-(4′-diphenylcarbinol-5′-menthyloxy-butyrolatone)}

A novel compound of chiral spiro{1-bromo-4-hydroxy-5-N-cyclohexyl-butyro-lactam-6-oxo-dirings3.1.0hexane-2,3′-(4′-diphenylcarbinol-5′-menthyloxy-butyrolatone)} was synthesized via tandem nucleophilic substitution reaction under mild conditions=and its structure was determined by IR =1H NMR=elemental analysis and X-ray diffraction.The crystal structure of this compound is of monoclinic system=space group P21 with a=9.7356(9)=b=12.2760(12)=c=14.9577(14)=β=101.0300(10)°=Mr=680.66=Z=2=V=1754.6(3)3=Dc=1.288 g/cm3=μ(MoKα)=1.216 mm-1=F(000)=716=the final R=0.0434 and wR=0.0996.     

Synthesis and Crystal Structure of 1,4-Dimethyl-2,5-di{[2’-(3-pyridylmethylamino-formyl)phenoxyl]methyl}benzene Perchlorate

The title compound, 1,4-dimethyl-2,5-di{[2’-(3-pyridylmethylaminoformyl)phenoxyl]- methyl}benzene perchlorate (C36H36Cl2N4O12, Mr = 787.59), has been synthesized and structurally determined by single-crystal X-ray diffraction. The crystal crystallizes in the orthorhombic system, space group Pbca with a = 14.366(4), b = 15.159(4), c = 16.443(5), V = 3580.9(17)3, Z = 4, Dc = 1.461 g/cm3, μ = 0.253 mm-1, F(000) = 1640, R = 0.0618 and wR = 0.1525 for 1615 observed reflections (I > 2σ(I)). In the structure of the title compound, a two-dimensional supramolecular layer is formed via intermolecular hydrogen bonding interactions.     

Synthesis, Structure and Physical Properties of a Barium（II） Complex with 5-Sulfoisophthalic Acid Sodium

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).     

Synthesis and Crystal Structure of (7R,8S,9S,12S)-13,14-dehydro-1-(4'-fluorobenzyloxy)-N-methyl-2,13-dimethoxy-12-hydroxymorphinane

The title compound (7R,8S,9S,12S)-13,14-dehydro-1-(4-fluorobenzyloxy)-N-methyl-2,13-dimethoxy-12-hydroxymorphinane was synthesized by the reaction of O-4-bromobenzyl-sinomenine with lithium aluminum hydride.Its chemical structure was determined by X-ray single-crystal diffraction.The crystal belongs to triclinic,space group P1 with M r=439.51,a=7.7236(1),b=8.7282(1),c=9.9342(2),α=81.176(1),β=67.43,γ=64.577(1)°,μ=0.76 mm-1,V=558.45(2)3,Z=1,D c=1.307 mg/m 3,F(000)=234 and T=133 K.     

Synthesis, Crystal Structure and Fungicidal Activity of (E)-2-[(4-tert-Butyl-5- (4-methoxybenzyl)thiazol-2-ylimino)methyl]phenol

The title compound(E)-2-(4-tert-butyl-5-(4-methoxybenzyl)thiazol-2-ylimino)me-thylphenol was synthesized by the reaction of 5-(4-methoxybenzyl)-4-tert-butylthiazol-2-amine with salicylaldehyde=and its crystal structure was determined by single-crystal X-ray diffraction.The crystal belongs to the monoclinic system=space group P21/c with a=5.9362(8)=b=11.5070(15)=c=29.460(4)=β=97.326(3)°=V=1995.9(5)3=Z=4=F(000)=808=C22H24N2O2S=Mr=380.49=Dc=1.266 g/cm3=S=1.031=μ=0.181 mm--1=the final R=0.0474 and wR=0.1441 for 4327 observed reflections(I > 2σ(I)).Intramolecular O-H…N hydrogen bond is observed in the crystal.The preliminary bioassay showed that the title compound exhibits 95% inhibition rate against Rhizoctonia solani at the test concentration of 500 mg/L.     

Synthesis and Crystal Structure of [K（2,2,2-crypt）]_3Sb_（11）

The title complex [K(2,2,2-crypt)]3Sb11 has been prepared by the reaction of K3Cd2Sb with Cu-C≡CH in ethylenediamine in the presence of 2,2,2-crypt, and characterized by low temperature X-ray structure analysis. The crystal is of orthorhombic system, space group C2221 with a = 15.475(3), b = 22.807(5), c = 24.834(6), V = 8765(3)3, Dc = 1.960 g/cm3, C54H108K3N6O18Sb11, Mr = 2586.01, F(000) = 4944, μ = 3.531 mm-1, Z = 4, R = 0.0442 and wR = 0.1053 for 10265 observed reflections (I > 2σ(I)). The "naked" Sb113- anion is stable due to the completely sequestered alkali metal cations through ion-ion interactions.     

Synthesis and Crystal Structure of Methyl 2-(Diphenylamino)-4-phenyl-1,3-thiazole-5-carboxylate

The title compound, methyl 2-(diphenylamino)-4-phenyl-1,3-thiazole-5-carboxylate, was synthesized and studied by single-crystal X-ray diffraction method. The structure of the product was confirmed by IR, 1H- and 13C-NMR spectroscopy and elemental analysis. These experimental studies were supported by quantum mechanical calculations. The structure was solved in monoclinic, space group P21/c with a = 9.573(3), b = 19.533(7), c = 9.876(3), β = 92.35(4)°, V = 1845.2(10)3, T = 85(2) K, Z = 4, R = 0.040 and wR = 0.089 for 6424 observed reflections withI>2σ(I).     

Synthesis and Crystal Structure of a Zinc(II) Complex with 2-(4′-Chlorine-benzoyl)-benzoic Acid and 1,10-Phenanthroline

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(11), b = 18.3140(17), c = 30.961(3), V = 6850.7(11)3, C80H48Cl4N4O12Zn2, Mr = 1529.76, Dc = 1.483 g/cm3, μ(MoKα) = 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.     

Synthesis and Crystal Structure of a Manganese（Ⅱ） Complex with 2-（4′-Chlorine- benzoyl）-benzoic Acid and 1,10-Phenanthroline

A new metal-organic complex Mn2（cbba）4（phen）2 （Hcbba = 2-（4＇-chlorine-benzoyl）- benzoic acid, phen = 1,10-phenanthroline） 1 has been hydrotherrnally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses and IR spectroscopy. The compound crystallizes in orthorhombic, space group Pbcn with α = 12.154（5）, b = 18.166（7）, c = 31.197（13） A, V = 6887（5） A^3, C80H48Cl4Mn2N4O12, Mr= 1508.90, Dc = 1.455 g/cm^3, μ（MoKα） = 0.591 mm^-1, F（000） = 3080, Z = 4, the final R = 0.0408 and wR = 0.0873 for 4033 observed reflections （I 〉 2σ（I））. In the crystal structure, the manganese atom is six-coordinated with four carboxylate oxygen atoms from three different cbba ligands and two nitrogen atoms from phen ligands, showing a distorted octahedral geometry. Furthermore, it exhibits a 3D supramolecular network through π-π interactions.     

Synthesis, Crystal Structure and Photoluminescence of a 2D Two-fold Interpenetrating Cd(Ⅱ) Coordination Polymer Based on a Flexible Reduced Schiff Base Ligand

<正>By the reaction of cadmium chloride with a reduced Schiff base ligand (H_2L = N-(4- carboxybenzyl)-glycine), a novel Cd(II) compound [Cd(HL)_2]·4H_2O (1) has been obtained. Single-crystal X-ray diffraction analysis reveals that it crystallizes in orthorhombic, space group Pbcn with a = 13.9788(8), b = 24.4204(14), c = 13.9580(8), V = 4764.8(5)~3, Z = 8, M_r = 600.84, D_c = 1.675 g/cm~3, μ = 0.983 mm~(-1), F(000) = 2448, S = 1.084, R = 0.0806 and wR = 0.1705 (I > 2σ(I)). It displays a 2D two-fold interpenetrating structure. The Cd(II) ions are six-coordinated. The cross-linkage of Cd(II) ions by the bridge of HL anions results in a [Cd(HL)_2] layer. Every two [Cd(HL)_2]_n layers are penetrated with each other, resulting in a two-fold interpenetrating double-layer structure by π-π stacking interactions and hydrogen bonds. Such double-layers are further linked by hydrogen bonds into a supramolecular structure. Photoluminescent investigation shows that compound 1 displays strong emission in the purple region.