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 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.

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） A, β = 93.50（3）°, V = 4840.5（17） 3, C36H30Mo8N10O26Zn, Mr = 1851.59, Dc = 2.541 g/cm^3, 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）2^2＋ 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 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.

Syntheses,Structures,and Luminescent Properties of Zinc(Ⅱ)and Silver(Ⅰ)Complexes Based on 1-(4′-Carboxylatobenzyl)-3-(pyrazin-2-yl)pyrazole

Two novel coordination compounds, [Zn（CBPP）2（H2O）2]·3H2O（1） and[Ag（CBPP）·2H2O]（2）（HCBPP = 1-（4？-carboxylatobenzyl）-3-（pyrazin-2-yl）pyrazole）, were hydrothermally synthesized and characterized. Compound 1 crystallizes in monoclinic, space group C2 with a = 26.221（4）, b = 8.4211（7）, c = 14.295（3）A, β = 114.561（8）°, V = 2705.9（2） A3, Dc = 1.587 g/cm3, C28H28Cl2N8O9 Zn, Mr = 685.97 F（000） = 1416, μ（Mo Kα） = 0.926 mm-1, Z = 4, R = 0.0287, w R = 0.1076 for 2818 observed reflections（I 〉 2σ（I））, and R = 0.0300, w R = 0.1110 for all data. In 1, each deprotonated CBPP-ligand with a bidentate coordination mode connects two Zn（II） atoms to generate a 1D helical chain along the b axis. The adjacent chains intersect with each other through hinged Zn（II） ions to build up an interesting two-dimensional network. Compound 2 crystallizes in monoclinic, space group P21/n with a = 6.3544（1）, b = 11.7195（3）, c = 19.3188（4）A, β = 94.297（2）°, V = 1434.64（5） A3, Dc = 1.894 g/cm3, C14H13 Ag N4O4, Mr = 409.15 F（000） = 816, μ（Mo Kα） = 11.536 mm-1, Z = 4, R = 0.0456 and w R = 0.1184 for 2402 observed reflections（I 〉 2σ（I））, and R = 0.0517, w R = 0.1275 for all data. In 2, each ligand binds two Ag（I） atoms in a tridentate coordination mode to form an infinite zigzag chain. Their thermal and photoluminescent properties were also investigated.

Hydrothermal Syntheses and Crystal Structures of Six Complexes Constructed from 1,3,5-Benzenetricarboxylic Acid and 4'-(4-Pyridyl)-2,2':6',2''-terpyridine Mixed Ligands

Six new transition metal complexes, [Zn（HBTC）（PYTPY）]n·n PYTPY（1）, [Cu（HBTC）（PYTPY）]n·n PYTPY（2）, [Co（HBTC）（PYTPY）]n·n DMF（3）, [Mn（HBTC）（PYTPY）]n·n DMF（4）, [Cd（HBTC）（PYTPY）（H2O）]n·2nH2O（5）, and [Co（HBTC）（PYTPY）（H2O）2]（6）,（H3BTC = 1,3,5-benzenetricarboxylic acid, PYTPY = 4＇-（4-pyridyl）-2,2＇：6＇,2＇＇-terpyridine, DMF = N,N？-dimethylformamide）, have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction. Complexes 1~5 all feature one-dimensional chain structures, and complex 6 exhibits a zero-dimensional structure. Complexes 1~5 present three-dimensional（3D） supramolecular frameworks via π-π stacking interactions, whenas 6 has also a 3D supramolecular structure assembled by hydrogen bonding. Meanwhile, complexes 1 ~ 6 exhibit the thermal stabilities and photoluminescent properties.

Synthesis, Crystal Structure, Fluorescent Property and DFT Calculations of a New Zn(Ⅱ) Complex Based on 3-(2-Pyridyl)-5-(4-pyridyl)-1H-1,2,4-triazole

A new coordination compound Zn（2,4＇-bpt）2（H2O）（1） based on the versatile ligand 2,4＇-Hbpt（2,4？-Hbpt = 3-（2-pyridyl）-5-（4-pyridyl）-1H-1,2,4-triazole） was prepared by hydrothermal reactions. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, X-ray powder diffraction, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis indicates that the complex belongs to monoclinic system, space group C2/c with a = 23.877（3）, b = 0.7483（9）, c = 1.2492（2） A, b = 92.681（2）°, V = 2230.6（4） A^3, Z = 4, Dc = 1.572 g/cm^3, m = 1.143 mm^-1, Mr = 527.85 and F（000） = 1080. The final R = 0.0581 and wR = 0.0898 with I 〉 2s（I）. 1 is a 0D motif which is connected by hydrogen bonds to form a corrugated 1D pattern. In addition, 1 shows strong photoluminescent emissions in the solid state at room temperature which can be used as potential optical materials. Theoretical calculations based on density functional theory（DFT） were employed in order to explicate the stability and chemical reactivity of 2,4＇-Hbpt with different conformations. The results indicated that conformation I is more stable and prior to coordination in the reactions.

2D-QSAR Studies on Pyrazole Compounds Containing Pyrimidine Amino

The quantitative structure-activity relationship （QSAR） of 16 pyrazole compounds was studied by ab initio method at the HF/3-21G level using Guassian03 soft. The optimized structures together with some characteristic and electric parameters of the title compounds were obtained; some stereo-parameters were calculated by HyperChem software. Stepwise multiple regression method was adopted to establish bi- and tri-parametric models between biological activity and some parameters. The lager △E and logP, the higher biological activity; and the biological activity would be promoted with the smaller μ, QN and QPYRA. It provided a theory direction to synthesize some compounds with high activity.

Synthesis and Crystal Structure of (2S,5S)-1-Aza-2- (2-pyridyl)-3-oxa-4,4-diphenylbicyclo [3.3.0] Octane

The title compound (C23H22N2O) 3 has been synthesized by the reaction of (S)- (-)-1,1-diphenyl-2-pyrrolidinemethanol 1 with 2-pyridinecarboxaldehyde 2 in refluxing benzene catalyzed by TsOH, and its structure was determined by single-crystal X-ray diffraction. The crystal belongs to orthorhombic, space group P212121 with a = 8.4747(8), b = 10.8829(10), c = 19.777(2) , Mr = 342.43, V =1824.0(3) 3, Dc = 1.247 g/cm3, Z = 4, m = 0.077 mm-1 and F(000) = 728. The structure was solved by direct methods and refined by full-matrix least-squares techniques to the final R = 0.0497 and wR = 0.0927.

Synthesis and Crystal Structure of a 2D Sm(Ⅲ) Coordination Polymer: {[Sm_2L_3(H_2O)_4]·(4,4?-bpy)·3H_2O}_n

A new compound, {[Sm^2L3（H2O）4]·（4,4＇-bpy）·3H2O}n（1, H2 L = 5-（3-pyridyl methoxy） isophthalic acid, 4,4＇-bpy = 4,4A-dipyridyl）, has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in triclinic, space group P1 with a = 11.266（2）, b = 15.530（3）, c = 16.711（3） A, α = 112.803（3）, β = 90.526（1）, γ = 94.006（3）°, V = 2686.6（9） A3, Z = 2, Dc = 1.727 g/cm^3, μ = 2.251 mm-1, F（000） = 1392, S = 0.999, the final R = 0.0296 and wR = 0.1058. In the title compound, two crystallographically independent Sm^3＋ cations are bridged by the carboxyl group of L2- ligands to form two different {Sm^2} binuclear subunits which are further connected by two distinct L2- ligands to shape a 1D chain, and such 1D chains are linked up to generate a 2D coordination polymer by another crystallographically unique L2- ligand. The thermogravimetric analysis and luminescent property of the title compound were also investigated.

Synthesis,Structure,and Magnetic Property of One Snake-shaped Copper(Ⅱ)-organic Compound:Cu[Cu_2(PP)_2](CBPC)_2]·2(H_2O)

One novel copper（II）-organic compound,namely Cu[Cu2（PP）2]（CBPC）2]·2（H2O）（1,H2CBPC = 1-[（2＇-carboxybiphenyl-4-yl）methyl]-2-propylimidazole-4-carboxylic acid,HPP = 3-（2-pyridyl）pyrazole）,was designed and synthesized under hydrothermal conditions.X-ray diffraction analysis reveals that two Cu（II）ions in the quasi-planar dimmer of [Cu2（PP）2] are linked by the carboxylate oxygen atoms on the phenyl ring and the imidazole ring,respectively,yielding one snake-shaped structure.Magnetic measurements reveal that compound 1 shows the strongly antiferromagnetic property.Crystal data of 1：C58H52Cu3N10O10,Mr = 1239.72,monoclinic,P21/c,a = 14.900（7）,b = 15.029（7）,c = 12.308（6）,β = 102.519（9）o,V = 2691（2）3,Z = 2,Dc = 1.530 g/cm3,F（000）= 1274,μ = 1.246 mm-1,R = 0.0416,wR = 0.0780（I 2σ（I））and S = 0.999.

Hydrothermal Synthesis and Crystal Structure of One Novel 1-D Copper(Ⅱ)-organic Framework:{[Cu_2(PP)_2(CBPC)]_2·7H_2O}_n

One novel 1-D copper（Ⅱ）-organic compound,namely {[Cu2（PP）2（CBPC）]2·7H2O}n（1,H2CBPC=1-[（2＇-carboxybiphenyl-4-yl）methyl]-2-propylimidazole-4-carboxylic acid,HPP=3-（2-pyridyl）pyrazole）,was synthesized under hydrothermal conditions.X-ray diffraction analyses reveal that the two Cu（Ⅱ） ions in the distorted dimer [Cu2（PP）2] of 1 are linked by the carboxylate oxygen atoms on the phenyl and imidazole rings,respectively,forming one interesting snake-like chain.Single-crystal X-ray analyses reveal that it crystallizes in monoclinic,space group C2/c with a=30.656（8）,b=12.715（3）,c=22.405（5）,β=122.758（3）°,V=7344（3）3,Z=4,Mr=1681.65,Dc=1.521 g/cm3,F（000）=3464,μ=1.221 mm-1,the final R=0.0453 and wR=0.1023 for 4617 observed reflections with Ⅰ 〉2σ（Ⅰ）.

Synthesis and Crystal Structure of One Mixed-ligand Coordination Polymer Based on the Novel Terphenyl-2,5,2',5'-tetracarboxylic Acid Ligand

Solvothermal reaction of aromatic terphenyl-2,5,2＇,5＇-tetracarboxylic acid （Hnqptc） ligand and the transitional metal cation of Mn11 in the presence of 3-（2-pyridyl）pyrazole （pp） affords one new coordination polymer, [Mn（qptc）0.5（pp）2]n·n（H2O） （1）. The structure has been determined by single-crystal X-ray diffraction analyses and further characterized by elemental analyses, IR, TGA, and magnetism. The carboxyl groups of qptc4 exhibit a μ1-η1：η0 coordination mode, and the qptc4- acts as a H-shaped ligand linking the Mn11 centers together to form a 2D polymeric [Mn（qptc）0.5]n layer. The crystal of 1 crystallizes in orthorhombic, space group Pbca with a = 9.3119（12）, b = 20.848（3）, c = 26.134（3） A, V= 5073.4（11） A3, Z= 8, C27HIgMnN6O5,Mr=562.42, Dc = 1.473 g/cm3, F（000） = 2304 and μ（MoKa） = 0.571 mm-1. The final R = 0.0468 and wR = 0.1196 for 4429 observed reflections with I 〉 2σ（I） and R = 0.0797 and wR = 0.1383 for all data.

Hydrothermal syntheses and structural characterizations of three polyoxomolybdates frameworks linked by M(HL)_2 units(M=Co,Ni,Zn;L=3-(2-pyridyl)pyrazole)

Three polyoxomolybdate compounds,namely {[MII(HL)2]2(Mo8O26)}n(M = Co(1),Ni(2),Zn(3))(HL,3-(2-pyridyl)pyrazole),were designed and synthesized under the hydrothermal conditions and characterized by elemental analysis,IR spectroscopy,and TGA.Single-crystal X-ray diffraction analysis results reveal that compounds 1-3 own the isostructural chain structure consisting of the β-[Mo8O26]4- anions,which are linked by M(HL)22+ units via the terminal oxygen atoms.TGA curves show that the organic ligands separate from the related compounds above ca.673 K.

A New Co(Ⅱ)Coordination Compound Constructed by Tripyridyltriazole and Pyromellitic Acid:Synthesis,Crystal Structure and Antifungal Activity

A new coordination compound, [Co（L223）2（H2O）2]·H2pm（1, L223 = 3,4-bis（2-pyridyl）-5-（3-pyridyl）-1,2,4-triazole and H4 pm = pyromellitic acid）, has been synthesized. The structure of complex 1 has been characterized by X-ray single-crystal diffraction, elemental analysis, IR spectrum analysis and thermogravimetric analysis. Single-crystal X-ray diffraction analysis reveals that complex 1 belongs to the triclinic system, space group P1 with a = 10.2470（8）, b = 10.2879（9）, c = 10.2951（11） ？, α = 109.398（2）, β = 97.6590（10）, γ = 95.3260（10）°, V = 1003.60（16） ？3, Z = 1, Dc = 1.565 g/cm^3, μ = 0.508 mm%^-1, Mr = 945.73, F（000） = 485, the final R = 0.0562 and w R = 0.0783 with I 〉 2σ（I）. Two L223 as chelating ligands link one Co（II） ion to form a 0D motif. Furthermore, the 0D motifs are linked into a 2D coordination pattern with hydrogen bonds. In addition, the antifungal effects of the ligand and the complex were evaluated by the disc diffusion method against Colletotrichum gloeosporioides Penz. 1 represents antifungal activity with high levels of inhibitory potency which is larger than the corresponding ligand.