Two Coordination Polymers Constructed by Cd(Ⅱ) and Zn(Ⅱ) with in situ Generated 5-(3-Pyridyl)tetrazolate Ligand:Syntheses,Crystal Structures and Luminescence Properties

Hydrothermal reactions of 3-cyanopyridine and Na N3 with Zn Cl_2 or Cd Cl_2·5/2H_2 O in the presence of 1,4-benzenedicarboxylic acid(H2bdc) yielded two new coordination polymers,{[Zn(3-ptz)(bdc)_(0.5)(H_2O)_2]n·2H_2O}_n(1) and [Cd_2(3-ptz)_2Cl_2]_n(2),based on in situ synthesized 5-(3-pyridyl)tetrazolate(3-ptz-) organic ligand.They have been structurally characterized by elemental analysis(EA),infrared spectroscopy(IR) and single-crystal/powder X-ray diffraction(PXRD).In 1,two Zn(Ⅱ) ions are linked together through two μ_2-(3-ptz-) ligands to form a dimeric unit of [Zn(μ_2-3-ptz)(H_2O)_2]_2~(2+),which is further connected with other equivalent units by μ_2-bdc~(2-)spacers,resulting in an infinite 1D polymeric chain of [Zn_2(3-ptz)_2(H_2O)_2(bdc)]_n,and then strong hydrogen bonding interactions extend these 1D chains into a 3D supramolecular structure.In 2,the Cd(Ⅱ) ions are connected through μ_4-(3-ptz-) ligands and Cl-anions,leading to infinite 2D layers of [Cd_2(3-ptz)Cl_2]_n~(n+),which are further linked by another μ_4-(3-ptz-) pillared ligand to form a 3D layered-pillared framework architecture of [Cd)2(3-ptz))2Cl)2])n.Furthermore,thermal stability of these compounds was measured by thermogravimetric analysis(TGA) and their photoluminescent properties were also investigated in the solid state at room temperature.     

One Novel Mn(Ⅱ) Complex with 1-Substituted-1H-1,2,3-triazole-4-carboxylic Acid:Crystal Structure,Fluorescence and Hirshfeld Surface Analysis

The crystal structure of one novel Mn(II) complex, [Mn(pmta)_3]_2[Mn(H_2O)_6]·4H_2O(1), is reported(Hpmta = 5-methyl-1-phenyl-1H-1,2,3-triazole-4-carboxylic acid). In the title compound, the asymmetric unit consists of a [Mn(pmta_)3]ˉ anion, half [Mn(H_2O)_6]~(2+) counter cation and two lattice H_2O molecules, and the intra- and intermolecular hydrogen bonds connect the complex into a supramolecular structure. The liquid-state fluorescence spectra of complex 1 have been determined. Hirshfeld surface analysis was also studied. The main intermolecular interactions in the complex are O···H and H···H contacts.     

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.     

Hydrothermal Synthesis and Crystal Structure of a One-dimensional Coordination Polymer Constructed from Bicapped Pseudo-Keggin Cluster:(Et_3N)_(0.5)(en)_2[SiMo_(12)O_(40)(VO)_2]·4H_2O

A new pseudo Keggin-type bicapped compound(Et3N)0.5(en)2[SiMo12O40(VO)2]·4H2O(Et3N=triethylamine,en=ethylenediamine) has been hydrothermally synthesized and characterized by IR,elemental analysis,TG and X-ray crystallography.The title compound crystallizes in monoclinic,space group P21/n with a=17.576(2),b=13.535(1),c=21.587(2),β=103.790(10)°,V=4987.3(8)3,Z=4,Dc=2.925 Mg/m3,Mr=2196.12,F(000)=4148,μ=3.400 mm-1,R=0.0379 and wR=0.1219.The most remarkable structural feature of the compound is that the clusters represent bicapped pseudo-Keggin structure and are linked one by one through V-O-V bonds forming an infinite 1D chain.Furthermore,such chains are interconnected in a cross-like arrangement through multiform hydrogen bonds to yield a 3D supramolecular network.     

Two Metal Ion-controlled Zn(Ⅱ)/Cd(Ⅱ) Coordination Polymers Based on 1,3,5-Benzenetricarboxylic Acid

Two new coordination polymers {[Zn(Hbtc)(bpyb)]·H_2O}n(1) and {[Cd(Hbtc)-(bpyb)_(1.5)]·0.5 bpyb}_n(2)(H_3btc = 1,3,5-benzenetricarboxylic acid, bpyb = 1,4-bis(4-pyridyl)benzene) have been synthesized under hydrothermal conditions. The two compounds were characterized by elemental analysis, IR spectroscopy, and X-ray single-crystal diffraction. Compound 1 displays a 2-fold interpenetrating 3D supramolecular architecture through O–H···N/O hydrogen bonds and π-π stacking interactions. Compound 2 exhibits a 2D→3D polycatenated structure, which is further stabilized by O–H···N hydrogen bonds. The results indicate that the metal ion has significant effects on the formation and structure of the resulted coordination polymers. Furthermore, thermal stability and photoluminescent properties of 1 and 2 are also discussed in detail.     

Syntheses,Structures,and Properties of Two New Coordination Polymers Based on Tetracarboxylate and 2,2′-Bipyridine Mixed Ligands

Two new coordination polymers {[Zn2L1(2,2'-bpy)2(H2O)2]·4H2O}n(1) and [Zn2L2(2,2'-bpy)2(H2O)2]n(2)(H4L1 = terphenyl-2,2',4,4'-tetracarboxylic acid, H4L2 = quarterphenyl-2,2',4,4'-tetracarboxylic acid, and 2,2'-bpy = 2,2'-bipyridine) have been synthesized and characterized by elemental analysis, IR and X-ray single-crystal diffraction studies. Complex 1 displays 2D wavelike networks, which are further joined together through O–H···O hydrogen bonds to give a 3D supramolecular network. Complex 2 exhibits 1D ladder-like chains, and they are further joined together by π-π stacking and O–H···O hydrogen bonding interactions to form a 3D supramolecular network. The results indicate that the backbone of carboxylate ligands has significant effects on the formation and structure of the resulting functional coordination polymers. Additionally, thermal stability and photoluminescent properties of 1 and 2 are also investigated in detail.     

Syntheses,Structures and Properties of Two Mn(Ⅱ) Clusters Based on 1,10-Phenanthroline-2,9-dicarbaldehyde Dioxime Ligand

Two novel clusters [Mn~Ⅲ_3(μ_3-O)(phendox)3]X·13H_2O(X = Cl(1), Br(2]) have been obtained from the solvothermal reactions of 1,10-phenanthroline-2,9-dicarbaldehyde dioxime(H_2phendox) with MnCl_2·4H_2O or anhydrous MnBr_2, and their structures were characterized by elemental analysis, FT-IR, XRD, TGA, MS and single-crystal X-ray diffraction. It crystallizes in trigonal, space group P3_1/c. X-ray analysis reveals that the neighbouring [Mn_3(μ_3-O)(phendox)_3]+ cores are linked by C–H···Cl hydrogen bonds and form an infinite supramolecular chain along the c-axis. Neighbouring chains are packed with each other by off-set p-p interactions of the aromatic rings on phenox2-. A 3D supramolecular architecture in a honeycomb topology is formed with 1D hexagonal channel in the dimensions of 13? × 13? along the c-axis. The gas adsorption studies show that compound 1·13H_2O is stable upon the removal of guest molecules and the desolvated compound absorbed considerable amount of CO_2.     

Two Cd(Ⅱ) and Cu(Ⅱ) Complexes Based on 1-Butylbenzimidazole: Crystal Structures and Weak Interactions

1-Butylbenzimidazole L reacted with Cd(NO3)2·4H2O to afford complex [CdL(NO3)3H2O]·[HL] 1. The heptacoordinated Cd(Ⅱ) center adopts a distorted pentagongal bipyramidal geometry, and complex [CdL(NO3)3H2O]-entity and the protonated benzimidazium salt [HL]+ are connected via N-H···O hydrogen bond to form a dimeric unit [CdL(NO3)3H2O]·[HL]. A 3-D supramolecular network of 1 is formed through N-H···O and O-H···O hydrogen bonds together with π-π stacking interactions. Reaction of L with CuCl2 afforded a mononuclear complex, [CuL2Cl2] 2, in which the tetracoordinated Cu(II) center adopts a distorted tetrahedral geometry. In contrast, 2-D supramolecular layers of 2 are formed by C-H···Cl hydrogen bonds. The fluorescent emission spectra of L, 1 and 2 are described.     

Synthesis,Characterization and Molecular Structure of a Diiron Complex(μ-SCH_2CH_2CH_2S-μ)Fe_2(CO)_5(Ph_2PCH_3)

The title complex,(μ-pdt)Fe_2(CO)_5(Ph_2PCH_3)(pdt = SCH_2CH_2CH_2S),was obtained by the reaction of the parent complex(μ-pdt)Fe_2(CO)_6 with Ph_2PCH_3 and Me_3NO·2H_2O in good yield(90%). The title complex was characterized by IR,~1H NMR,~(31)P{~1H} NMR and ~(13)C{~1H} NMR spectroscopy as well as by single-crystal X-ray diffraction analysis. The molecular structure shows that the title complex contains a butterfly diiron propanedithiolate cluster with five terminal carbonyls and a monophosphine ligand Ph_2PCH_3. The crystal packing diagram reveals that intermolecular C H···O hydrogen bonds between CH_2 and carbonyls,π-π stacking interactions and van der Waals' interactions stabilize the solid state to form a three-dimensional network.     

Synthesis and Crystal Structure of a New Charge-assisted Hydrogen-bonded Host Framework [Co(en)_3]_2[Zr_2(C_2O_4)_7]·2H_2O

Using the deep eutectic solvent formed of oxalic acid and choline chloride, a new charge-assisted hydrogen-bonded host framework [Co(en)3]2[Zr2(C2O4)7]·2H2O(1) has been obtained. The title complex crystallizes in the monoclinic, space group P21/n(No. 14) with a = 7.7448(10), b = 14.5683(19), c = 19.375(3), β = 92.124(2)o, V = 2184.5(5) 3, Z = 4, Dc = 1.996 g.cm-3, F(000) = 1332, μ = 1.328 mm-1, R = 0.0353 and w R = 0.0718(Ⅰ 2σ(Ⅰ)). Single-crystal structure analysis reveals that the title complex possesses a 3D network assembled through a multitude of charge-assisted hydrogen bonds between the in situ generated anionic coordination complexes [Zr2(C2O4)7]6- and metal complexes Co(en)33+.     

Syntheses,Crystal Structures and Antibacterial Activities of Cobalt(Ⅱ) and Manganese(Ⅱ) Complexes with Schiff Base Ligand Derived from Tryptamine

Two new mononuclear complexes, namely [Co(L)_2](1) and [Mn(L)_2](2)(HL = N-(3-methylsalicylidene)tryptamine), have been synthesized by the reactions of the ligand with cobalt acetate or manganese acetate in anhydrous ethanol. The crystal structures of the complexes were characterized by IR spectrum, elemental analysis, PXRD and single-crystal X-ray diffraction analysis. Complex 1 crystallizes in monoclinic, space group C2/c, with a = 23.146(2), b = 9.4864(10), c = 13.9261(15) ?, β = 102.898(2)°, V = 2980.6(5) ?3, Z = 4, Dc = 1.367 g/cm3, F(000) = 1284 and μ = 0.616 mm-1. Complex 2 crystallizes in monoclinic, space group P21/n, with a = 14.807(11), b = 13.118(10), c = 16.663(13) ?, β = 111.237(14)°, V = 3017(4) ?3, Z = 4, Dc = 1.342 g/cm~3, F(000) = 1276 and μ = 0.477 mm-1. The units of complex 1 are linked by intermolecular N–H···π hydrogen bonds into infinite 1D chains, which are further extended into a 3D supramolecular structure by a series of π···π stacking interactions. The units of complex 2 are linked by intermolecular N–H···π hydrogen bonds and C–H···π hydrogen bonds into an infinite 3D supramolecular structure. Meanwhile, the antibacterial activities of the ligand and its complexes have been tested against four kinds of bacteria. The results show that the three compounds all have excellent antibacterial activities and that 1 and 2 possess stronger inhibiting effects against the bacteria than the Schiff base.     

V(HSO_4)_3 promoted oxidation of alcohols and trimethylsilyl,tetrahyropyranyl and methoxymethyl ethers with Cu(NO_3)_2·3H_2O in the absence of solvent

V(HSO_4)_3 has been found to be an efficient reagent for the promotion of the oxidation of alcohols and trimethylsilyl, tetrahydropyranyl and methoxymethyl ethers to their corresponding carbonyl compounds with Cu(NO_3)_2·3H_2O in the absence of solvent.     

Synthesis and Crystal Structure of a New Complex Zn(Ⅱ)L_2·2CH_3OH(H_2L = 4-Chloro-2-(2,3-dihydro-1H-benzoimidazol-2-yl)-phenol)

A new complex Zn(Ⅱ)L2·2CH3OH(H2L = 4-chloro-2-(2,3-dihydro-1H-ben-zoimi-dazol-2-yl)-phenol) has been prepared and characterized by single-crystal X-ray diffraction analysis and elemental analysis.The crystal is of triclinic system,space group P1 with a = 9.2905(10),b = 10.3555(13),c = 14.9590(14) ,α = 101.0340(10),β = 101.261(2),γ = 99.1660(10)o,V = 1356.1(3) 3,Z = 2,C28H24Cl2N4O4Zn,Mr = 616.78,Dc = 1.510 g/cm3,μ = 1.145 mm·1,F(000) = 632,the final R = 0.0379 and wR = 0.0830 for 3606 observed reflections with I 2σ(I).The Zn(Ⅱ) atom presents a distorted square pyramidal coordination involving two H2L ligands.The hydrogen bonds and π···π stacking interactions extend the complex into a two-dimensional framework.     

Synthesis and Crystal Structure of a New Mixed-ligand Cluster[Mo3O4(C2O4)2bipy-(H2O3)]·EtOH·2H2O(bipy=2,2'-Bipyridine)

The novel mixed-ligand neutral compound [Mo3O4(C2O4)2·bipy(H2O)3]·EtOH·2H2O (bipy = 2,2'-bipyridine) has been prepared by the reaction of oxalic acid elution of Mo(Ⅳ) and bipy, and characterized by single-crystal X-ray diffraction analysis and IR. The crystal is of triclinic, space groups P1 with a = 9.5520(2), b = 10.3730(1), c = 13.5722(2) (A), α = 74.940(12), β = 80.772(14), γ = 69.898(11)°, V = 1215.73(11) (A)3, Z = 2, C16H24Mo3N2O18, Mr = 820.19, Dc = 2.241 g/cm3, μ = 1.616 mm-1, F(000) = 808, T= 293(2) K, the final R = 0.0424 and wR = 0.0939 for 4119 observed reflections with Ⅰ> 2σ(Ⅰ). The trinuclear unit is coordinated by mixed ligands of oxalate and bipy. The intermolecular hydrogen bonding interactions among adjacent [Mo3O4(C2O4)2·bipy(H2O)3] extend the compound into a therr-dimensional supramolecular framework. The uncoordinated water molecules and ethal molecules act as space-fillers and consolidate the whole architecture through hydrogen bonding interactions.     

Hydrothermal Syntheses and Crystal Structures of Zn(Ⅱ) and Co(Ⅱ) Complexes Constructed from 5-Methoxyisophthalic Acid and 1,10-Phenanthroline Ligands

Two new one-dimensional coordination polymers,[Zn(L)(phen)]n 1 and {[Co2(L)2(phen)2]·2H2O}n 2(H2L=5-methoxyisophthalic acid,phen=1,10-phenanthroline),have been obtained by hydrothermal conditions.According to their single-crystal X-ray diffraction analyses,complex 1 crystallizes in the monoclinic system,space group P2/c with a=8.9195(11),b=12.3620(15),c=17.0211(18),β=106.690(5)o,V=1797.7(4)3,the final R=0.0298 and wR=0.0715 for 3351 independent reflections with Rint=0.0353.Complex 2 crystallizes in the monoclinic system,space group C2/c with a=24.981(4),b=11.1204(19),c=18.125(3),β=132.5620(10)o,V=3708.5(11)3,the final R=0.0349 and wR=0.0914 for 3424 independent reflections with Rint=0.0214.Both 1 and 2 show L-bridged one-dimensional chain.1 and 2 are further assembled by π-π and hydrogen bonding interactions into 2-D layer structures,and they also display 3-D supramolecular frameworks through their other hydrogen bonds.Zn(Ⅱ) ion is five-coordinated with a distorted trigonal bipyramidal coordination geometry,while Co(Ⅱ) ion is six-coordinated and resides in a distorted octahedral coordination geometry.Additionally,complex 1 shows fluorescence in the solid state at room temperature.     

Synthesis and Characterization of a Trinuclear Zinc(Ⅱ) Complex with Schiff Base (1R,2R)-(-)-Diaminocyclohexane- N,N'-biscarboxyl-salicylidene)

A homochiral complex, Zn3(Hsalen)2(Py)4(H2O)2 (salen = (1R,2R)-(-)-diamino-cyclohexane-N,N'-biscarboxyl-salicylidene) 1, has been synthesized by solvothermal procedure and characterized by IR, microanalysis, TGA, powder and single-crystal X-ray crystallography. It crystallizes in monoclinic space group P2 with a = 10.9439(7), b = 10.1722(6), c = 27.3450(17), β = 97.5060(10)o, V = 3018.1(3) 3, Z = 2, Zn3(Hsalen)2(Py)4(H2O)2, Mr = 1363.33, Dc = 1.500 g/cm3, F(000) = 1408, μ = 1.257 mm-1, GOOF = 1.042, the final R = 0.0601 and wR = 0.1464 for 10322 observed reflections with I 2σ(I). The coordination polymer 1 possesses a 1D infinite zigzag chain architecture constructed by strong hydrogen bonding interactions and the polymeric chains are further assembled into a 2D supramolecular network structure via C-H···π interactions between the cyclohexane and aromatic rings of the ligand of adjacent chains. Simultaneously, π···π stacking interactions play an important role in forming the 2D supramolecular framework.     

A New 1D Cd(Ⅱ) Coordination Polymer Constructed by 2,2'-H_2biimidazole:[Cd(H_2biim)_2(SO_4)]_n·3nH_2O

A new 1D Cd(II) coordination polymer, [Cd(H2biim)2(SO4)]n·3n H2O(1, H2 biim = 2,2'-H2biimidazole), has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/c with a = 6.8405(14), b = 17.792(4), c = 14.987(3) A, β = 92.68(3), V = 1822.1(6) A3, Z = 4, C12H18 Cd N8O7S, Mr = 530.80, Dc = 1.935 g/cm3, F(000) = 1064, μ(Mo Ka) = 1.371 mm-1, R = 0.0280 and w R = 0.0617. In 1, adjacent Cd(II) atoms are bridged by sulfate anions in bidentate modes to yield a 1D chain. H2 biim ligands are located on both sides of the chain in chelating bidentate modes. Further, the H2 biim ligands from neighboring chains are paired through π-π interactions to generate a supramolecular layer, which is stabilized by the complicated N–H···O and O–H···O hydrogen bonds. In addition, thermal behavior and luminescent property of 1 have been investigated.     

Hydrothermal Synthesis,Structural Investigation and Characterization of an Organic-inorganic Hybrid, [Co(BⅡM)_3]_2H[BW_(12)O_(40)]·7H_2O

An organic-inorganic hybrid based on α-Keggin-typed [BW12O40]5- anionic cluster, [Co(BⅡM)3]2H[BW12O40]·7H2O(BⅡM = 2,2′-biimidazole), was hydrothermally synthesized and structurally characterized by thermogravimetric analysis, IR and UV spectra. The title compound crystallizes in monoclinic, space group P21/n with a = 12.3490(10), b = 33.270(3), c = 18.9660(16) β = 105.9950(10)°, V = 7490.5(11) 3, C36H50BCo2N24O47W12, Mr = 3905.80, Dc = 3.451g/cm3, μ(MoKα) = 18.886 mm-1, F(000) = 6972, Z = 4, S = 1.004, the final R = 0.0404 and wR = 0.0914 for 14683 observed reflections(I 2σ(I)). The compound consists of two isolated [Co(BⅡM)3]2+ cations and one [BW12O40]5- anion, in which each Co2+ ion is coordinated by six N atoms from three BⅡM ligands displaying a regular CoN6 octahedron. These components are finally linked together via N–H···O(polyoxometalate and water) hydrogen bonds into a two-dimensional framework. Full investigation of the intermolecular interactions by Hirshfeld surface and fingerprint plots clearly indicates that there are rare W–Oterminal···πimidazole ring interactions which cooperate with the classical N–H···O hydrogen bonds to stabilize the structural packing.     

Synthesis,Crystal Structure and Luminescence of a New Zn(Ⅱ) Dimer: [Zn(bpdc)(L)]_2·4H_2O

A new dimeric compound, [Zn(bpdc)(L)]2·4H2O(1, L = 11-fluoro-dipyrido[3,2-a:2',3'-c]phenazine and bpdc = 1,1'-biphenyl-2,2'-dicarboxylate), has been synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group C2/c with a = 23.671(5), b = 22.547(5), c = 13.741(3), β = 123.47(3)o, V = 6118(2) 3, Z = 4, C66H44Cl2F2N8O12Zn2, Mr = 1380.73, Dc = 1.499 g/cm3, F(000) = 2816, μ(MoKa) = 0.949 mm-1, R = 0.0572 and wR = 0.1620. In 1, Zn1 and the symmetry formed Zn1 ions are connected by four bridging bidentate carboxylate groups from two independent bpdc anions to yield a binuclear unit with the Zn···Zn separation by bpdc anions of 4.168. Two L ligands are located on both sides of the dimer in chelating bidentate modes. The lateral L ligands from neighboring dimers are paired through strong π-π interactions to result in a fascinating 1D ladder-like supramolecular array. In addition, neighboring supramolecular ladders are packed each other to yield a 3D supramolecular architecture with a 1D channel.     

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.