π-π Stacking and Magnetic Coupling Mechanism on a Mono-nuclear Mn(Ⅱ) Complex

A new mono-nuclear Mn(Ⅱ) complex [Mn(MPT)2(NCS)(HOCH3)]ClO4(MPT = 2-methoxyl-1,10-phenanthroline) has been synthesized with 2-methoxyl-1,10-phenanthroline and thiocyanate anion as ligands,and its crystal structure was determined by X-ray crystallography.The crystal data:monoclinic system,space group P21/c with a = 12.8849(17),b = 15.684(2),c = 14.2703(19) ,β = 92.126(2)°,V = 2881.9(7) 3,Z = 4,C28H24ClMnN5O7S,Mr = 664.97,Dc = 1.533 g/cm3,F(000) = 1364 and μ = 0.679 mm-1.In the crystal,MPT functions as a bidentate ligand and Mn(Ⅱ) ion assumes a distorted octahedral geometry.In the crystal there are two types of π-π stacking interactions among the adjacent complexes,which involves 1,10-phenanthroline rings.The theoretical calculations reveal that the two types of π-π stacking resulted in a weak anti-ferromagnetic coupling with 2J =-14.68 cm-1 and a weak ferromagnetic coupling with 2J = 0.70 cm-1,respectively.The theoretical calculations also reveal that there are both spin polarization and spin delocalization in the two π-π stacking systems,and the magnetic coupling signs are unable to explain with McConnell I spin-polarization mechanism.     

Ionothermal Syntheses and Crystal Structures of Two Cobalt（Ⅱ） Compounds：Co（2,2＇-bpy）_2Br_2 and Co（1,10-phen）_2Br_2

Two cobalt(Ⅱ) compounds,Co(2,2-bpy) 2 Br 2 (1,2,2-bpy=2,2-bipyridyl) and Co(1,10-phen) 2 Br 2 (2,1,10-phen=1,10-phenanthroline),have been prepared under ionothermal reactions using the 1-propyl-3-methylimidazolium bromide ionic liquid solvent.Single-crystal X-ray analyses reveal that 1 crystallizes in a monoclinic space group P2 1 /c,with a=8.5509(13),b=14.804(2),c=15.650(2),β=97.119(2) o,V=1965.8(5) 3,Z=4,C 20 H 16 Br 2 N 4 Co,M r=531.12,D c=1.795 g/cm 3,μ=4.950 mm-1,F(000)=1044,the final R=0.0467 and wR=0.0736 for 2291 observed reflections with I > 2σ(Ⅰ).Complex 2 crystallizes in a monoclinic space group P2 1 /n,with a=10.4237(8),b=16.8657(12),c=12.4945(9)b,β=102.110(1) o,V=2147.7(3) 3,Z=4,C 24 H 16 Br 2 N 4 Co,M r=579.16,D c=1.791 g/cm 3,μ=4.540 mm-1,F(000)=1140,the final R=0.0431 and wR=0.1042 for 3470 observed reflections with I > 2σ(Ⅰ).The mononuclear molecules of 1 are linked by the C-H···Br hydrogen bonds and π-π interactions to form a three-dimensional supramolecular framework structure.The C-H···Br hydrogen bonds and π-π interactions link the mononuclear molecules of 2 to give a two-dimensional layer structure.     

Syntheses,Crystal Structures and Luminescent and Magnetic Properties of Cerium(Ⅲ) and Zinc(Ⅱ) Coordination Compounds Constructed from 3,5-Dibromobenzoic Acid

Two coordination compounds, namely [Ce(3,5-Br2BC)3(3,5-HBr2BC)]n(1) and [Zn(3,5-Br2BC)2(phen)](2, 3,5-HBr2 BC = 3,5-dibromobenzoic acid, phen = 1,10-phenanthroline), were assembled. Single-crystal X-ray diffraction studies show that compound 1 possesses a 1D chain coordination network, which is further extended into a 3D supramolecular architecture via Br···Br and Br···O halogen bonding. Compound 2 consists of a mononuclear molecule, which is assembled to a 3D supramolecular framework through C–H···O hydrogen bond, π-π stacking interactions and Br···π halogen bonding. Luminescent and magnetic properties of both compounds have also been studied.     

Synthesis,Crystal Structure and Evaluations of Its Cytotoxicity,Anti-microbial and Anti-hydroxyl Radical Activities of a New Co-crystal Compound(C_6H_6Cl_2N_2O_2S)·(Phen)·H_2O

Co-crystal is a very potential kind of drug solid forms, and has a far-reaching influence on designing and preparing drugs. A new 1:1:1 co-crystal compound consisting of 4-amino-3,5-dichloro-benzenesulfonamide, 1,10-phenanthroline and water was synthesized, and its crystal structure was characterized by X-ray diffraction method. The compositions of the co-crystal are self-assembled into a three-dimensional network structure via intermolecular interactions including hydrogen bonds, π-π stacking, Cl???Cl interactions and van der Waals' forces. According to the evaluations of cytotoxicity assays, anti-microbial and anti-hydroxyl radicals, this co-crystal is a potential drug.     

A Fluorescent Cadmium-organic Framework Constructed by m-Thioacetatebenzoic Acid

Reactions of Cd(OAC)2·2H2O with m-thioacetatebenzoic acid(H2L) and 1,10-phenanthroline(phen) give rise to a metal-organic framework,[CdL(phen)]n(1).X-ray single-crystal diffraction reveals that 1 crystallizes in the monoclinic system,space group C2/c,with a= 25.7099(5),b=10.3872(2),c=19.1820(4),β=131.114(1)°,V=3859.4(1)3,Mr=502.80,Z= 8,F(000)=2000,μ=1.271 mm-1,Dc=1.731 g·cm-3,the final R=0.0226 and wR=0.0559 for 3817 observed reflections(Ⅰ > 2σ(Ⅰ)).1 displays a 1D double-strand chain structure with crab-like dinuclear subunits,and extends into a 3D network by π-π interactions and C-H···O hydrogen bonds.Photoluminescence studies reveal that it displays intense structure-related fluorescent emission bands(λex=342 nm) at 370.5 and 389 nm in the solid state at room temperature.     

Synthesis and Crystal Structure of a New Mn（Ⅱ） Coordination Polymer Based on Asymmetric Semi-rigid V-shaped Dicarboxylate

A novel manganese(Ⅱ) coordination polymer with 2-(4-carboxyphenoxy) benzoic acid (2,4'-H2oba) and 1,10-phenanthroline (1,10-phen) has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction, IR and elemental analysis. Compound [Mn(2,4'-oba)(1,10-phen)] is of monoclinic system, space group P21/n with a = 7.960(1), b = 15.464(2), c = 18.703(3) , β = 99.976(2)°, V = 2267.5(6) 3, Z = 4, Mr = 491.35, Dc = 1.439 g/cm3, F(000) = 1004 and μ = 0.623 cm·1. The final R = 0.0419 and wR = 0.0978 for 3444 observed reflections with I > 2σ(I). X-ray diffraction analysis reveals that the oba2-ligands adopt a bis(chelating bidentate) mode to link two Mn(Ⅱ) centers to form an infinite 1D helical chain. Furthermore, a 3D supramolecular structure was formed by π-π stacking interactions and hydrogen bonds.     

Detection of NO2 Based on 4-Carboxyl-4'-hydroxy Azobenzene and Its Cu(Ⅱ) Complex

<正>An organic ligand and its Cu(II) complex formulated as (C_(13)H_(10)N_2O_3)·5H_2O (H_2L·5H_2O, 1) and Cu(HL)_2(phen)·0.125H_2O (2, H2L = 4-carboxyl-4′-hydroxy azobenzene, phen = 1,10-phenanthroline) have been synthesized and structurally characterized by single-crystal X-ray diffraction. In the two compounds, H_2L and HL exhibit a trans-conformation. Complex 2 shows a mononuclear Cu(II) structure with the hydroxyl group of HL uncoordinated. Complex 2 is assembled into a three-dimensional (3D) supramolecular architecture by hydrogen bonds and π-π stacking interactions. H_2L and compound 2 can detect NO_2 via reversible and irreversible color changes, respectively. The mechanism for the color changes is investigated.     

Synthesis,Crystal Structure and Recognition Properties of 2-（5-（4-Chlorophenyl）-1-phenyl-4,5-dihydro-1H-pyrazol-3-yl）pyridine

The title compound 2-(5-(4-chlorophenyl)-1-phenyl-4,5-dihydro-1H-pyrazol-3-yl)- pyridine(C20H16ClN3, Mr = 333.81) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to monoclinic, space group P21/n with a = 10.9925(12), b = 11.0378(12), c = 14.2751(18) , β = 98.074(11)°, V = 1714.9(3)3, Z = 4, Dc = 1.293 g/cm3, μ(MoKα) = 0.228 mm-1, F(000) = 696, the final R = 0.0521 and wR = 0.1349 for 3495 observed reflections with I 2σ(I). Intermolecular C–H...π interactions and π-π stacking interactions stabilize the crystal structure. The binding study by fluorescence spectroscope titration showed that the title compound can selectively recognize Fe3+ in THF solution with fluorescence quenching.     

Crystal Structure of a Two-dimensional Coordination Polymer [Ba2（phen）4（tp）2]n

A novel two-dimensional coordination polymer [Ba2(phen)4(tp)2]n(phen=1,10-phenanthroline,tp=terephthalic acid) has been synthesized with tp as bridge ligands and structurally determined by X-ray crystallography.The crystal belongs to the monoclinic system,space group C2/c,with a=18.877(4),b=18.489(4),c=15.658(3),β=103.61(3)o,V=5311.5(19)3,C32H20O4N4Ba,Mr=661.86,Z=8,F(000)=2624,μ=1.542mm-1,Dc=1.655 g/cm3,the final R= 0.0228 and wR=0.0554 for 6063 observed reflections(I2σ(I)).The structural analysis shows that each tp ligand bridges barium atoms to form a two-dimensional infinite layer.There are aromatic π-π stacking interactions between neighboring layers,and aromatic π-π interactions further extend such layers into a three-dimensional supramolecular framework.     

Synthesis and Structure of 1.5Zn(phen)_3·L·3NO_3 Supramolecule(phen=o-Phenanthroline,L=4-Aminoacetophenone Thiosemicarbazone)

A supramolecular framework,1.5Zn(phen)3·L·3NO3(C63H48Zn1.5N16O9S),has been synthesized.The ligand L was synthesized by the condensation of p-aminoacetophenone with thiosemicarbazide.The crystal belongs to the monoclinic system,space group C2/c,with a = 31.005(2),b = 15.114(2),c = 24.887(3) ,β = 94.260(2)o,Z = 8,V = 11630(2) 3,Dc = 1.489 g/cm3,Mr = 1303.29,λ(MoKα) = 0.71069 ,μ = 0.735 mm-1,F(000) = 5368,Rint = 0.0699,R = 0.0505 and wR = 0.0707.Two independent Zn atoms are both coordinated by six N atoms from three phen ligands.π-π and C-H···π interactions among the L ligands and Zn(phen)3 cations,π-π and C-H···π interactions among the Zn(phen)3 cations and N-H···O hydrogen bonds among the L ligands and nitrate anions connect the whole structure into a 3-D supramolecular framework.     

Synthesis and Crystal Structure of 1-（4-Fluorophenyl）-2-hexylthiobenzo[4,5]-furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5（1H）-one

The crystal structure of the title compound 1-(4-fluorophenyl) -2-hexylthio-benzo [4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a]pyrimidin-5(1H) -one(C23H21FN4O2S,Mr = 436.5) has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic,space group P21/n with a = 13.9854(3) ,b = 17.2678(4) ,c = 18.1828(5) ,β = 99.364(2) °,V = 4332.58(18) 3,Z = 4,Dc = 1.338,F(000) =1824,μ = 0.185 mm-1,MoKa radiation(λ = 0.71073) ,R = 0.0538 and wR = 0.1162 for 4728 observed reflections with I > 2σ(I) . X-ray diffraction analysis reveals the fused rings of benzo[4,5]furo[3,2-d]-1,2,4-triazolo[1,5-a] pyrimidin-5(1H) -one system are nearly coplanar. The crystal packing is mainly stabilized by weak intermolecular C-H···O hydrogen bond and π-π interactions.     

Synthesis,Crystal Structure and Properties of Ethyl 3,9-Dimethyl-7-phenyl- 6H-dibenzo[b,d]pyran-6-one-8-carboxylate

Ethyl 3,9-dimethyl-7-phenyl-6H-dibenzo[b,d]pyran-6-one-8-carboxylate(C24H20O4, Mr = 372.40) has been synthesized and its structure was determined by 1H and 13C NMR, ESI-MS, elemental analysis, and X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P21/n, with a = 8.3674(11), b = 10.6683(14), c = 11.3817(15) , α = 95.596(2), β = 109.866(2), γ = 94.495(2)°, V = 944.2(2)3, Z = 2, Dc = 1.310 g/cm3, μ = 0.089 mm-1, F(000) = 392, R = 0.0482 and wR = 0.1281 for 2916 observed reflections with I 2σ(I). In the crystal structure, the fused tricyclic nucleus of the title compound is not fully coplanar. Analysis of the crystal packing indicates aromatic π-π stacking interactions occurring between the fused tricyclic aromatic rings of neighboring molecules in which a maximum overlap of the π-electron systems was achieved. Fluorescence and thermal studies indicate that compound 3 has good optical properties and thermal stability.     

Synthesis and Crystal Structure of N-(1'-H-Pyrrol-2'-ylcarbonyl)-5-amino-1,10-phenanthroline

The title compound,N-(1'-H-pyrrol-2'-ylcarbonyl)-5-amino-1,10-phenanthroline,was synthesized by the reaction of a-pyrrolyl carbonyl chloride and 5-amino-1,10-phenanthroline in pyridine.Determined by X-ray structure analysis,it crystallizes in triclinic system,space group P(1)with the following crystallographic data:C20H21N5O3,Mr=379.42,a=7.8559(4),b=9.1681(6),c =14.6818(9)(A),α=73.254(10),β=88.938(15),γ=68.080(10)°,V=934.66(10)(A)3,Z=2,F(000)=400.Dc=1.348 g/cm3 and μ=0.094 mm-1.The final R=0.0680 and wR=0.1419 for 2142observed reflections with I＞2σ(I),and R=0.1084 and wR=0.1643 for all reflections.Two aromatic ring planes(pyrrole and phenanthroline rings)are connected by the amide plane.Two title complex molecules are connected through hydrogen bonds and weak π-π stacking interactions to generate a 3-D supramolecule.     

Hydrothermal Synthesis and Crystal Structure of a 1D Cu（II） Coordination Polymer： [Cu（bbpy）（H_2bptc）]_n Constructed by a Tetracarboxylic Acid

The title compound [Cu(bbpy)(H2bptc)]n (bbpy = 4,4'-dimethyl-2,2'-bipyridine and H4bptc = 1,1'-biphenyl-2,2?,3,3'-tetracarboxylic acid) has been synthesized by hydrothermal reaction, and its structure was determined by X-ray diffraction and characterized by elemental analysis, IR spectrum and thermogravimetric analysis. The crystal is of triclinic, space group P1 with a = 11.2831(12), b = 11.6718(13), c = 11.7771(13), α = 105.392(2), β = 108.382(2), γ = 112.397(2)o, CuC28H20N2O8, Mr = 576.00, V = 1222.4(2)3, Dc = 1.565 g/cm3, F(000) = 590, μ = 0.951 mm-1, S = 1.022 and Z = 2. The final refinement gave R = 0.0405 and wR = 0.1142 for 4270 observed reflections with I > 2σ(I). The title complex has a 1D [Cu(bbpy)(H2bptc)]n chain structure, in which the extensive hydrogen-bond interactions make the chain more stable. The neighboring parallel chains are further packed into a 2D layer structure via π···π stacking interaction between the pyridine rings of bbpy ligands. Moreover, the adjacent layers are interconnected by the C-H···π interactions to form a 3D metal-organic framework.     

Synthesis, Crystal Structure and Fungicidal Activity of （Z）-3,3-Dimethyl-1-（1H-1,2,4-triazol-1-yl）butan-2-one O-2-Chlorobenzyl Oxime Nitrate

The title compound has been synthesized by the reaction of 3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-one oxime with 2-chlorobenzyl chloride, and then treated with 65～68% HNO3. Its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 14.5481(8), b = 9.3351(5), c = 13.1911(7) , β = 98.9450(10)°, Z = 4, V = 1769.67(17) 3, Mr = 369.81, Dc = 1.388 g/cm3, S = 1.06, μ = 0.247 mm-1, F(000) = 776, the final R = 0.0352 and wR = 0.0960 for 3069 observed reflections (I > 2σ(I)). X-ray crystal structure presents the intramolecular N–H…O hydrogen bond. The packing is nearly parallel without π-π stacking interactions between two adjacent phenyl rings and stabilized by Van der Waals force. The preliminary bioassay shows that the title compound possesses fungicidal activity against Gibberella zeae at the dosage of 25 mg/L.     

Synthesis,Crystal Structure and Biological Activity of 2-（Anthracen-9-yl）-5-p-tolyl-1,3,4-oxadiazole

A novel compound,2-(anthracen-9-yl)-5-p-tolyl-1,3,4-oxadiazole(C23H16N2O),has been synthesized by the condensation of 4-methylbenzohydrazide and anthracene-9-carbaldehyde in an ethanol solution with chloramine-T.The compound was characterized by 1H-NMR,13C-NMR,MS and single-crystal X-ray diffraction.The crystal belongs to the triclinic system,space group P with a = 7.7817(4),b = 8.8544(5),c = 12.4726(8) ,β = 92.8520(10)°,Z = 2,V = 826.58(8) 3,Dc = 1.352 g/cm3,Mr = 336.38,λ(MoKα) = 0.71073 ,μ = 0.084 mm-1,F(000) = 352,R = 0.0381 and wR = 0.1099.The dihedral angle between anthracene skeleton and phenyl ring is 64.19°.A total of 6354 unique reflections were collected,of which 3172 with I > 2σ(I) were observed.X-ray analysis indicated an offset face-to-face π-π stacking interaction between anthracene skeletons and an offset face-to-face π-π stacking interaction between phenyl ring planes.The novel compound molecules are connected through the offset face-to-face π-π stacking interactions to generate a three-dimensional network.The preliminary bioassay results showed that the novel compound exhibited significant insect growth inhibitory activity against Spodoptera litura Fabricius larvae.     

Synthesis,Crystal Structure and Spectral Property of a Water-bridged Co(Ⅱ) Coordination Polymer with 3-Flavonoxylacetic Acid Ligand

A new cobalt complex with flavonoid carboxylate ligand was synthesized and characterized. X-ray diffraction data revealed that the compound crystallizes in the monoclinic crystal system, space group P2_1/c with a = 7.936(3), b = 21.475(7), c = 20.010(7) ?, β = 102.856(14)o, V = 3325(2) ?~3, Z = 4, C_(34)H_(32)CoO_(15), M_r = 739.53, D_c = 1.477 g/cm~3, F(000) = 1532, μ = 0.591 mm~(-1), R = 0.1123 and w R = 0.1419. In the crystal structure, the Co(Ⅱ) shows 6 coordination geometry, and the flavonoid ligand coordinated with the Co(Ⅱ) ion in a monodentate mode. Hydrogen bonding interactions and π-π stacking interactions lead to the three-dimensional stacking of crystal and increase its stability. Moreover, the thermal stability and luminescent properties of the complex are also investigated. The fluorescence of the complex shows a great reduction of the intensity than that of the ligand.     

Synthesis and Crystal Structure of a New Iron Complex with Cyclic Water Hexamers [Fe(CDTA)(H_2O)]·[Fe(1,10-phen)_3]·10H_2O·2OH

The title complex [Fe(CDTA)(H2O)]·[Fe(1,10-phen)3]·10H2O·2OH (CDTA = transcyclohexane-1,2-diamine-N,N,N,N′-tetraacetate) has been prepared and characterized by single-crystal X-ray diffraction analysis. The crystal adopts space group P with a = 12.793(4), b = 14.104(5), c = 17.880(5), V = 2792.2(1)3, Dc = 1.459 g/cm3, C50H66Fe2N8O21, Mr = 1226.81, F(000) = 1284, μ = 0.604 mm-1, Z = 2, R = 0.1055 and wR = 0.2581 for 8675 observed reflections (I > 2σ(I)). X-ray crystallography analysis exhibits that the title compound consists of two crystallographically independent molecules [Fe(CDTA)(H2O)] and [Fe(1,10-phen)3], and they are connected through O-H···O hydrogen bonds and π···π stacking interactions forming a 3D supramolecular structure. Interestingly, there is a cyclic water hexamer with chair conformation in this complex.     

Synthesis and Crystal Structure of N-（1′-H-Pyrrol- 2′-ylcarbonyl）-5-amino- 1,10-phenanthroline

The title compound, N-（1′-H-pyrrol-2′-ylcarbonyl）-5-amino-1,10-phenanthroline, was synthesized by the reaction of a-pyrrolyl carbonyl chloride and 5-amino-1,10-phenanthroline in pyridine. Determined by X-ray structure analysis, it crystallizes in triclinic system, space group P1 with the following crystallographic data： C20H21N5O3, Mr = 379.42, a = 7.8559（4）, b = 9.1681（6）, c = 14.6818（9） A, α= 73.254（10）,β= 88.938（15）, γ= 68.080（10）°, V= 934.66（10） A3, Z = 2, F（000） = 400, Dc = 1.348 g/cm^3 and p = 0.094 mm-1. The final R = 0.0680 and wR = 0.1419 for 2142 observed reflections with I 〉 2σ（/）, and R = 0.1084 and wR = 0.1643 for all reflections. Two aromatic ring planes （pyrrole and phenanthroline rings） are connected by the amide plane. Two different types of intermolecular hydrogen bonds, O-H…N and N-H…O, exist in the crystal. The title complex molecules are connected through hydrogen bonds and weak π-π stacking interactions to generate a 3-D supramolecule.     

Synthesis and Crystal Structure of the Binuclear Complex:[Cu_2(phen)_2(ip)(Hip)_2]·4H_2O

A binuclear complex [Cu2(phen)2(ip)(Hip)2]·4H2O has been synthesized by the reaction of Cu(CH3COO)2·H2O, phen(1,10-phenanthroline) and isophthalic acid (H2ip) under hydrothermal condition. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. Crystal data for this complex: mono- clinic, space group C2/c, a = 19.214(3), b = 10.6973(14), c = 22.567(3) , β = 105.081(2)°, C24H19N2O8Cu, Mr = 526.95, Z = 8, F(000) = 2160, V = 4478.6(10) 3, Dc = 1.563 g/cm3, μ = 1.030 mm-1, –24≤h≤16, –13≤k≤13, –28≤l≤28, R = 0.0369 and wR = 0.0819 for 4615 (Rint = 1.0357) independent reflections and 3290 observed ones (I > 2σ(I)). Structural analysis shows that coordination geometry of Cu(Ⅱ) is a planar square, and the title complex exhibits a 2-D framework supramolecular structure by hydrogen bonds and π-π stacking interactions.