Syntheses,Crystal Structures and Intermolecular Interactions of Cu（II） Complexes with Methyl- benzoic Acid （MBA） and 1,10-Phenanthroline

Two cupric complexes containing methylbenzoic acid have been prepared and crystallized by solvent evaporation method in DMF. The single-crystal X-ray crystallographic analysis reveals that they are dicaryon complexes. Complex I with formula of [Cu2（m- MBA）4DMF2] crystallizes in monoclinic with space group of P21/c and complex 2 with formula of [Cuz（o-MBA）ffo-phen）2]·NO3·H2O crystallizes in triclinic with space group of P I. The weak interactions including C-H...O hydrogen bonds, C-H…π interactions and π-π stacking in the structures of two complexes are observed from the X-ray crystallographic data. In addition, there are still classical hydrogen bonds in 2. The different strength of intermolecular interaction in the structure is reflected on their different thermal stability measured by thermal gravimetric analysis and 2D-1R correlation spectroscopy of two complexes. The study of weak interactions is meaningful to provide supporting data for supramolecular chemistry theory and potential applications in molecular biology.     

Synthesis,Structure, and Luminescent Properties of Two Complexes Based on Flexible Phenylenediacetate Ligand

Two new Zn(Ⅱ) and Cd(Ⅱ) coordination complexes, [Zn(ppda)(idz)]_n(1) and [Cd(mpda)(mbib)]_n(2)(H2 ppda = 1,4-phenylenediacetic acid, H_2 mpda = 1,3-phenylenediacetic acid, idz = imidazole, mbib = 1,3-bis(imidazol-1-ylmethyl)benzene), have been synthesized by using Zn(Ⅱ)/Cd(Ⅱ) salt and phenylenediacetic acid in the presence of different imidazole ligands under hydrothermal conditions, and characterized by elemental analysis, IR spectroscopy, single-crystal X-ray crystallography and thermogravimetric analysis. Complex 1 crystallizes in orthorhombic system, Iba2 space group. The carboxylic acid ligands form a 2 D helical layer with Zn(Ⅱ) ions, and such layers are expanded into a 3 D network structure by the force of C–H×××π. Complex 2 crystallizes in monoclinic system, P2_1/n space group. Complex 2 shows a 3 D framework with two Cd(Ⅱ) ions as nodes of a dual-core unit, which can be considered to be 6-connected net and regarded as a rare(4~4,5~(10),7) topology network with self-interlacing. The structural diversities indicate that rigid and flexible imidazole ligands play dominating roles in modulating the formation of structures of these crystalline materials. Moreover, the luminescent properties of two complexes are investigated in solid state.     

Synthesis,Crystal Structures and Properties of Two Novel Co（Ⅱ） and Cd（Ⅱ） Complexes of N-AcetyI-L-glutamic Acid and Imidazole Ligands

Two novel complexes {[Co（A-glu）（Im）2]·0.5H2O}n （1） and [Cd（A-glu）（Im）3]n （2） （H2A-glu=N-acetyl-L-glutamic acid, Im=imidazole） have been synthesized from the reaction of H2A-glu with Co（CH3COO）2·4H2O or Cd（CH3COO）2·2H2O in the presence of Im. Both of the complexes display different coordination environment and similar one-dimensional chain structure. The magnetic susceptibility measurements for 1 show a weak antiferromagnetic interaction between two cobalt（Ⅱ） ions bridged by A-glu ligand. The complex 2 exhibits an intense fluorescent emission in solid state at room temperature.     

Syntheses and Crystal Structures of Three Cadmium（II） Coordination Complexes Based on Flexible 1,2-Bis（imidazol-1~ˊ-yl）ethane

Three Cd（II） coordination complexes,{[Cd（bime）3]（NO3）2·（H2O）3}n（1）,[Cd（bime）Br2]n（2） and [（H2bime）（CdBr4）（H2O）]n（3）（bime = 1,2-bis（imidazol-1-yl）ethane）,have been prepared and characterized.Single-crystal X-ray diffraction analysis reveals that 1~3 crystallize in the trigonal space group P-3,monoclinic space group C2/c and triclinic space group P1,respectively.In 1,bime bridges six-coordinated Cd（II） to generate a two-fold interpenetrating 3D coordination polymer,in which NO3- is not involved in coordination,but serves as a void filler to balance the charge of the 3D framework.The six NO3- and six uncoordinated water molecules form an unprecedented 24-membered macrocycle through hydrogen bonding interaction.In 2,bime in an anti-conformation links the CdBr2 units into a zigzag chain.In 3,bime does not take part in coordination,but is protonated to act as a counter cation of [CdBr4 ]2-.The hydrogen bonds between H2bime and [CdBr4]2- result in the formation of a supramolecular chain.     

Cis- and Trans-Coordination Assembly of Nitrogen Heterocycle with Copper（Ⅱ） and Silver（Ⅰ）

After the preparation of 1,4-bis（4,5-dihydro-lH-imidazol-2-yl）benzene（bdib）, a nitrogen heterocycle with potential coordination manners of both cis- and trans-configuration forms, three complexes, including cis-[Cuz（bdib ）2（/L-OCH3）2]Cl2·2MeOH（1）, trans-[Cu（bdib）（AcO）2]n（2）, and cis-[Ag2（bdib）2]（NO3）2.2H20（3）, were successfully self-assembled. Complexes 1 and 2 crystallized in the monoclinic system with P21/n space group and complex 3 in the triclinic system with P1 space group.     

A Novel 3D Heterobimetallic Cyano-bridged Coor- dination Polymer {（NH4）2[Cd（H20）Fe（CN）6]}n： Synthesis and Crystal Structure①

A novel heterobimetaUic coordination polymer, {（NH4）2[Cd（H20）Fe（CN）6]}n 1, has been synthesized by using the slow diffusion method and structurally characterized by elemental analysis, 1R spectroscopy and single-crystal X-ray diffraction. The crystal crystallizes in the monoclinic system, space group P21/n, a = 7.4202（16）, b = 14.939（3）, c = 10.868（2） A and ,8 = 91.660（3）°. For 1, five CN groups of Fe（CN）6]4- are involved in bridging. The polymer displays a 3D open microporous framework with 5-connected uninodal （46.64） topology.     

Syntheses and Structures of Two Cadmium Complexes with Isophthaloylbisglycine Acid and 4,4'-Bipyridine

The two title complexes [{Cd（IBG-CH3）（4,4＇-bipy）（H2O）2}·NO3]n 1 and [{Cd（IBG）- （4,4＇-bipy）（H2O）2}·2H2O]n 2 （H2IBG = isophthaloylbisglycine and 4,4＇-bipy = 4,4＇-bipyridine） have been synthesized and characterized by single-crystal structure determination,IR and TG analyses. Complex 1 crystallizes in monoclinic,space group C2/c with a = 27.221（2）,b = 11.6093（7）,c = 16.3571（9）A,V = 5149.2（6） A^3,Z = 8,C23H23N5O11Cd,Mr = 657.86,Dc = 1.697 g/cm^3,F（000） = 2656.00,μ（MoKα） = 0.919 mm^-1,the final R = 0.0478 and wR = 0.0882 for 3728 observed reflections with I 〉 2σ（I）. Complex 2 crystallizes in triclinic,space group Pī with a = 9.0940（4）,b = 11.6852（5）,c = 13.1119（6）A,V = 1230.26 A^3,Z = 2,C22H26N4O10Cd,Mr = 618.87,Dc = 1.671 g/cm^3,F（000） = 628.0,μ（MoKα） = 0.951 mm^-1,the final R = 0.0567 and wR = 0.1124 for 3713 observed reflections with I 〉 2σ（I）. In both structures,the CdII metal centers are coordinated by seven atoms to form a distorted pentagonal bipyramidal geometry.     

Synthesis,Crystal Structure and Photoluminescence of [Gd（C6NO2H5）3- （H2O）2]2n·（nH5O2）（nHgCl5）（2nHgCl4）·（2nH2O）

A heterometallic 4f-5d inorganic-organic metaMsonicotinato hybrid [Gd（C6NO2H5）3- （H2O）2]2n·（nH5O2）（nHgCl5）（2nHgCl4）·（2nH2O） 1 has been synthesized via hydrothermal reaction and structurally characterized. Complex 1 crystallizes in the space group C2/c of monoclinic system with four formula units in a cell： a = 24.234（8）, b = 20.816（7）, c = 15.333（3）A , β= 128.091（8）°, V = 6088（3）A^3, C36H47Cl13Gd2Hg3N6O20, Mr = 2260.92, Dc = 2.467 g/cm^3, S = 0.896, μ（MoKα） = 10.331 mm^-1, F（000） = 4216, R = 0.0344 and wR = 0.0629. The crystal structure analysis reveals that the title complex is characteristic of a one-dimensional chain-like structure. Photoluminescent investigation reveals that the title complex displays a broad and intense emission in the green region.     

Synthesis,Crystal Structure,and Magnetic and Water-induced Reversible Transformation Properties of {[Ni（IBG）（g-HeO）（HeO）e].2HeO}n

A novel NiII complex {[Ni（IBG）μ-H20）（H2O）2]·2H2O}n 1 （H2IBG = isophthaloyl- bisglycine） has been synthesized and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectra, and thermogravimetric analysis. It crystallizes in monoclinic, space group P2/c with a = 15.40（2）, b = 6.960（10）, c = 7.865（11） A, β = 90.32（3）°, F = 843（2） A3, Z = 2, C12H18NiN2Oll, Mr = 424.99, Dc = 1.675 g/cm3, F（000） = 440,/a（MoKa） = 1.214 mm-1, the final R = 0.0514 and wR = 0.1247 for 1078 observed reflections with I 〉 2σ（I）. In the structure, each NiH center is situated in the center of a rather regular octahedron. Moreover, thermal stability has been studied and magnetic measurements show antiferromagnetic interactions for this complex.     

Two New Metal-organic Frameworks Constructed from 3,4,5-Substituted-1,2,4-Triazole Ligands

Two new complexes,[Zn（L1）2（SCN）2]·H2O（1,L1 = 3,5-dimethyl-4-p-tolyl-4H1,2,4-triazole and [Cd3（L2）6（SCN）6]（2,L2 = 3,5-dimethyl-4-phenyl-4H-1,2,4-triazole）,have been hydrothermally prepared and characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental analysis and PXRD.Complex 1 crystallizes in monoclinic,space group P21 /n with a = 11.246（13）,b = 9.640（11）,c = 26.13（3）,β = 100.97（3）,V = 1108.5（3） 3,Z = 4,C24 H28 N8 OS2 Zn,Mr = 572.02,Dc = 1.366 g/cm3,μ = 1.065 mm-1,S = 0.992,F（000） = 1184,the final R = 0.0602 and wR = 0.1700 for 2925 observed reflections（I 2σ（I））.Complex 2 crystallizes in triclinic,space group P1 with a = 11.6669（3）,b = 12.0957（2）,c = 14.3674（3）,α = 105.380（3）,β = 91.020（2）,γ = 92.4100（10）o,V = 1952.30（7）3,Z = 1,C66H66N24S6Cd3,Mr = 1725.08,Dc = 1.467 g/cm3,μ = 1.025 mm-1,S = 1.037,F（000） = 870,the final R = 0.0336 and wR = 0.0946 for 7819 observed reflections（I 2σ（I））.In the title complexes,complex 1 is a mononuclear molecule where the centre Zn（II） coordinates to two 3,4,5-substituted 1,2,4-triazole ligands（L1） and two terminal SCN-anions in a tetrahedral environment while six-coordinated centre Cd（II） atoms with octahedral geometry in complex 2 are bridged by virtue of substituted 1,2,4-triazole（L2） in N1,N2-bridging mode and μ2-N,N-SCN-anions into a trinuclear molecule.     

Synthesis and Crystal Structures of Two Di-Cu(Ⅱ) Complexes Based on an Asymmetric Dinucleating Ligand

Two new dicopper(II) complexes [Cu2L(OAc)2](ClO4)·H2O(1) and [Cu2L(BPP)2]-(ClO4)(2) using an asymmetric dinucleating ligand HL and auxiliary ligands such as acetate(OAc) and bisphenyl phosphate(BPP) have been synthesized and characterized by elemental analysis, IR and single-crystal X-ray diffraction. Complex 1 crystallizes as blue single crystals that belong to the triclinic crystal system and P1 space group, while complex 2 crystallizes in a monoclinic P21/c space group. Single-crystal X-ray diffraction analysis reveals that the two copper ions in complexes 1 and 2 reside within the adjacent ligand compartments and are bridged by the endogenous phenoxo-O from ligand L and the introduction of two desired exogenous carboxylates or phosphates in the bidentate μ-1,3-bridged mode. The coordination geometries of Cu(1) and Cu(2) are both distorted square pyramids.     

A Diphenoxo-bridged Ferromagnetic Copper（Ⅱ） Dimer Based on N-（2-Hydroxybenzyl）salicylaldimine

A new dinuclear copper（Ⅱ） complex, [Cu（L）（py）]2 1 （H2L = N-（2-hydroxybenzyl）- salicylaldimine, py = pyridine）, has been synthesized and characterized by elemental analysis, IR and UV spectra. 1 crystallizes in space group P2 1/n with a = 8.2106, b = 10.715, c = 17.864A, β = 99.365°, V = 1550.7A3, Z = 4, C19H16CuN2O2, Mr = 367.88, Dc = 1.576 g/cm3,μ（MoKα） = 1.422 mm-1, F（000） = 756, the final R = 0.0280 and wR = 0.0746. Complex 1 is a centrosymmetric dimer with two copper（H） centers, two py ligands and two L2- ligands. Each L2- ligand donates its azomethine nitrogen and one of the phenolate groups to one copper（Ⅱ） ion and shares the other phenolate group between the two copper（H） ions, affording a Cu2O2 plane. Each copper（Ⅱ） center has a slightly distorted square pyramidal geometry with a bridging phenolate group at the apex. Magnetic studies suggest the presence of a weak ferromagnetic interaction Via two phenoxo bridges. The magnetic susceptibility data （2-300 K） of complex 1 were analyzed by means of H = -2JS1S2 -DSz. The least-squares fitting of the data to the theoretical equation leads to J = 10.3 cm-1, g = 2.03, D = 0.67 cm-1 and R = ∑（Xobsd -Xcalcd）2/∑Xobsd2= 2.76 × 10^-3.     

Construction of a 2D Cd（II） Coordination Polymer Based on a V-shaped Bidentate Ligand

A two-dimensional（2D）coordination polymer{[Cd（bdc）（dpb）]·H2O}n（1）has been prepared by solvothermal reaction of 1,3-dipyridyl benzene（1,3-dpb）with deprotonated1,4-benzenedicarboxylate（H2bdc）,and was characterized by elemental analysis,IR spectroscopy,and X-ray single-crystal diffraction.It crystallizes in the monoclinic system,space group C2/c with a=15.1839（12）,b=20.7585（17）,c=7.2989（6）,β=117.3450（10）°,V=2043.5（3）3,C24H18N2O5Cd,Mr=526.81,Dc=1.712 g/cm3,F（000）=1056.0,μ=1.110 mm-1and Z=4.The neighboring Cd（II）ions link the bdc2-anions and 1,3-dpb to form an infinite 2D sheet,and such two2D sheets are interlocked with each other to form a 2D→2D sheet.Two groups of interlocked sheets are further linked together by intermolecularπ···πinteraction,giving a 3D supramolecular network.In addition,the fluorescence property of 1 was also studied.     

Syntheses and Crystal Structures of Two Gd（Ⅲ） Hydrogen Supramolecules Based on p-Sulfonatothiacalix[4]arene

Two novel polymeric complexes, [Gd（HsTCAS）（H2O）7]·4H2O 1 and [Gd（HsTCAS） （CH3COCH3）（H2O）6]·6H2O 2 （H4TCAS = p-sulfonatothiacalix[4]arene）, have been synthesized and characterized by single-crystal X-ray diffraction analyses. Complex 1 crystallizes in monoclinic, space group C2/m with a = 20.2308（12）, b = 19.0894（10）, c = 12.2448（7）A, β = 101.847（3）°, V = 4628.1（5）A^3, C24H43GdO27S8, Mr = 1169.25, Z = 4, Dc = 1.690 g/cm^3, F（000） = 2380,μ = 1.879 mm^-1, the final R = 0.0404 and wR = 0.1038 for 5127 observed reflections with I 〉 2σ（I）. Complex 2 is pseudo-isostructural with complex 1.     

Structures and magnetic properties of several novel lanthanide coordination polymers based on thiophene-2,5-dicarboxylic acid

Eight novel lanthanide complexes: {Ln(TDA)1.5(H2O)2}n (Ln = Pr(1a), Nd(2a)) and {Ln(TDA)(Ac)(H2O)}n (Ln = Pr(1), Nd(2), Eu(3), Gd(4), Tb(5), Dy(6); TDA = Thiophene-2,5-dicarboxylic acid anion) have been constructed by hydrothermal reaction. Structural analyses reveal that complexes 1a and 2a belong to the space group C2/c, exhibiting three-dimensional (3D) frameworks. Complexes 1-6 with P21/c space group were prepared in the presence of excessive ammonium acetate, giving rise to interesting 3D frameworks different from those of 1a and 2a. Magnetic property studies of 4-6 reveal the weak antiferromagnetic interaction exists between adjacent Gd3+ in 4. The complex 6 displays rather rare slow magnetization relaxation behavior in 3D frameworks.     

Synthesis,Crystal Structure,and Thermal Stability of a Dibutyltin Complex {[4-Et2NC6H3（O）C=NC6H3（O）- 5-NO2]（n-Bu2Sn）}2 and Its Interaction with DNA

The Schiff base organotin(IV) complex {[4-Et2NC6H3(O)C=NC6H3(O)-5-NO2](nBu2Sn)}2 has been synthesized via the reaction between 4-(diethylamino) salicylaldehyde-2-amino-4-nitrophenol Schiff base(H2L) and dibutyltin oxide. Complex C1 has been characterized by IR, 1H NMR, 13 C NMR spectra, and elemental analysis, and its crystal structure was determined by X-ray diffraction. It crystallizes in the monoclinic system, space group P21/n with a = 15.6559(8), b = 9.1657(5), c = 18.8351(10) , β = 107.3440(10)°, Z = 4, V = 2579.9(2) 3, Dc = 1.442 Mg·m-3, μ(MoKα) = 1.025 mm-1, F(000) = 1152, R = 0.0250 and wR = 0.0633. The central Sn atom is coordinated in a hexadentate manner to assume a distorted octahedral configuration. Complex C1 was studied by TGA analysis in air atmosphere. The interaction between complex C1 and the herring sperm DNA was realized through the intercalation of the complex based on the studies by EB fluorescent probe.     

Synthesis, Spectroscopic and Electrochemical Investigations of Two vic-Dioximes and Their Mononuclear Ni（Ⅱ）, Cu（Ⅱ） and Co（Ⅱ） Metal Complexes Containing Morpholine Group

Two vic-dioxime ligands （LxH2） containing morpholine group have been synthesized from 4-[2-（dimethylaminoethyl）] morpholine with anti-phenylchloroglyoxime or anti-monochloroglyoxime in absolute THF at -15 ℃. Reaction of two vic-dioxime ligands with MCl2·nH2O （M： Ni, Cu or Co and n=2 or 6） salts in 1 ： 2 molar ratio afforded metal complexes of type [M（LxH）2] or [M（LxH）2·2H2O]. All of metal complexes are non-electrolytes as shown by their molar conductivities （Am） in DMF （dimethyl formamide） at 10^-3 mol·L^-1. Structures of the ligands and metal complexes have been solved by elemental analyses, FT-IR, UV-Vis, ^1H NMR and ^13C NMR, magnetic susceptibility measurements, molar conductivity measurements. Furthermore, redox properties of the metal complexes were investigated by cyclic voltammetry.     

Synthesis,Crystal Structure,and Photoluminescent and Semiconductive Properties of [La（C6NO2Hs）3-（H2O）2]2n·（nH5O2）（nHgCl5）（2nHgCl4）·（2nH2O）

A new heterometallic 4f-5d inorganic-organic metal-isonicotinic acid complex [La（C6NO2Hs）3-（H2O）2]2n·（nH5O2）（nHgCl5）（2nHgCl4）·（2nH2O） 1 has been synthesized via hydro- thermal reaction and structurally characterized. Complex 1 crystallizes in the space group C21c of monoclinic system with four formula units in a cell： a = 24.140（7）, b = 20.884（7）, c = 15.462（2）A, fl = 127.46（1）°, V = 6187（3）A3, C36HaTCl13Hg3La2N6020, Mr = 2224.24, Dc = 2.388 g/cm3, Z = 4, T = 293（2） K, μ（MoKa） = 9.401 mm-1, F（000） = 4160 and RIwR = 0.0376/0.0636 for 4130 observed reflections （I 〉 20（/）） and 5617 unique reflections. Complex 1 is characteristic of a one-dimensional polycationic chain-like structure. Photoluminescent investigation reveals that the title complex displays interesting emissions in violet and orange regions. The luminescence spectra show stronger orange emission than violet emission. Optical absorption spectra of 1 reveal the presence of a wide optical bandgap of 3.41 eV.     

A 2-Fold Interpenetrated Framework Assembled from Pyridine-3-carboxylate Ligand and Transition Metal:Synthesis,Structure and Photoluminescent Property

A novel cadmium（Ⅱ） coordination polymer [Cd2（3-pa）4（4,4＇-bpy）（H2O）].3.08H2O 1 has been synthesized by pyridine-3-carboxylate （3-pall） and CdO with exo-bidentate rigid dipyridyl ligand 4,4＇-bipyridine （4,4＇-bpy） by using a hydrothermal method, its structure was determined by single-crystal X-ray diffraction and its luminescent property was also documented. Complex 1 crystallizes in orthorhombic space group Pbcn with a = 21.4074（14）, b = 27.1119（18）, c = 12.3879（8） A, V = 7189.9（8） A3, Z = 8, C34H32.16Cd2N6O12.08, Mr= 942.85, Dc = 1.742 g/cms, p = 1.255 mm-1 and F（000） = 3766. The structure was solved by direct methods and refined to R = 0.0353 and wR = 0.0891 for 6278 observed reflections （I 〉 2σ（I））. The most prominent structural feature is the mutual interpenetration of two identical 3-D open frameworks via filling the large void space, which gives a 2-fold interpenetrating architecture during the self-assembly process.     

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.