Synthesis and Crystal Structures of the α and β Forms of Bis （salicylaldoxime） copper （ Ⅱ ） Complexes

IntroductionSalicylaldoxime can be used in chemically modi-fied glassy-carbon electrodes,and applied to the deter-mination of metals in water.It shows a very high recov-ery[1,2].Direct design of solid-state structures that en-compass frameworks such as grids,ladders,helicesand channels of a desired architecture is central to crys-tal engineering science[3,4].Each of the oxidationstates of copper displays a different stereochemistry,ofwhich Cu(Ⅱ)is the most representative example foritsd9elec…     

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 and Crystal Structure of Cobalt(Ⅱ) and Copper(Ⅱ) Complexes Involving L-Aamino Alcohols

Two novel L-amino alcohol coordination cobalt and copper complexes I and Ⅱ were obtained separately from the direct reaction of L-plenylglycinol with Co(Ⅱ) acetate tetrahydrate in anhydrous ethanol and L-leucinol with Cu(Ⅱ) chloride dihydrate in anhydrous methanol. The structures of I and Ⅱ were determined by single-crystal X-ray diffraction and further characterized by elemental analysis and IR. For I: [Co3(C51H66N3O16)]2(OAc), monoclinic, space group P21, a = 15.022(3), b = 14.242(3), c = 28.922(6) , β = 98.944(4)o, V = 6112(2) 3, Z = 4, Dc = 1.339 g/cm3, the final R = 0.0860 for 21906 observed reflections with I 2(I). For Ⅱ: Cu2[C24H58N4O7Cl]Cl, orthorhombic, space group P212121, a = 6.1861(13), b = 20.838(4), c = 28.274(6) , V = 3644.6(13) 3, Z = 4, Dc = 1.310 g/cm3, the final R = 0.0642 for 11106 observed reflections with I 2(I). The complexes were then used to catalyze the Henry reaction and catalytic activity determined by 1H NMR.     

Syntheses and Crystal Structure of [Cu（pyr）3].Hg2I6

1INTRODUCTIONThepolynucleard10metalcomplexesarepotentialluminescentsensormaterialsduetotheirattractivephotochemicalandphotophysicalpro-perties[1,2].Lowdimensionalmetal-organichalidecomplexeshavereceivedever-interestingattentioninrecentyearsfortheirpotentialapplicationsaselectronicandcatalyticmaterials[3,4].RecentlyHomo-metaloligomersandthechainsofcopperhavebeenreportedbyZubietaandthecoworkersviahydrothermalsyntheses[5,6].Theexistingexamplesofcopperwithmercuryareextremelyrare[7].Intherece…     

Syntheses, Crystal Structures and Magnetic Properties of a New Nitronyl Nitroxide Radical and Its Cu（II） Complex

A new compound （NIT-mNO2 = 4,4,5,5-tetramethylimidazoline-2-yl-（2＇-chlor-5＇- nitrophenyl）-3-oxide-l-oxyl） 1 and its complex （Cu（NIT-mNO2）（hfac）2） 2 have been synthesized and structurally and magnetically characterized. Complex 1 crystallizes in monoclinic, space group P211n with a = 10.6798（9）, b = 11.2705（9）, c = 12.9559（10）A, β = 107.3770（10）°, V = 1488.3（2） A^3, C13H15ClN3O4, Mr = 312.73, Z = 4, Dc = 1.396 g/cm^3, g（MoKa） = 0.276 mm^-1, F（000） = 652, the final R = 0.0606 and wR = 0.1773 for 3405 independent reflections with Rint = 0.0203. The nitronyl nitroxide unit （imidazoline ring） is not coplanar with the phenyl ring with the dihedral angle between them of 55.75°. The compound results in a 1-D zig-zag chain structure by intermolecular H-bond interaction. Compound 2 crystallizes in triclinic, space group Pi with a = 10.3699（10）, b = 10.6286（11）, c = 15.1683（15）A, a = 77.5330（10）, ,β = 773080（10）, y = 87.3420（10）＊, V = 1592.5（3） A^3, C23HITCIFI2N3O8Cu, Mr = 790.39, Z = 2, Dc = 1.648 g/cm^3, μ（MoKa） = 0.888 mm^-1, F（000） = 788, the final R = 0.0793 and wR = 0.2153 for 5794 independent reflections with Rint = 0.0196. The Cu（Ⅱ） ion is located at a center of symmetry, and each Cu（Ⅱ） is surrounded by six oxygen atoms at the vertices of a distorted tetragonal octahedron. Four of the six oxygen atoms belong to two hfac ligands and occupy the equatorial coordination sites, while the other two of NIT-mNO2 act as μ-1,5 bridge between the Cu（Ⅱ） ion, thus forming a 1-D chain structure. The magnetic susceptibility data indicate intermolecular antiferromagnetic interactions between compound 1 and intrachain ferromagnetic behaviors.     

Synthesis and Crystal Structure of a New Penta-coordinated Cu（II） Complex： Cu（C17H13F3O3）2·CsH5N

A new copper（II） complex 3, Cu（C17H13F3O3）2·C5H5N, has been synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group C2/c with a = 17.8511（7）, b = 17.4136（7）, c = 13.9425（7） A, β = 124.4830（10）°, V = 3572.5（3） A^3, Z = 4, C39H29CuF6NO6, Mr = 785.17,/7（000） = 1604, T = 292（2） K, Dc = 1.460 g/cm^3 and p = 0.691 mm^-1. The structure was refined to R = 0.0477 and wR = 0.1110 for 2935 observed reflections with I 〉 2σ（I）. For the title compound, X-ray analysis reveals that the copper（II） is penta-coordinated by four oxygen atoms from the corresponding 1-（4-（benzyloxy）phenyl）-4,4,4-trifluorobutane-1,3-dione ligands and one nitrogen atom of pyridine, forming a distorted square pyramidal geometry. It is found that the trifluoromethyl group, F（1）/F（1＇）, F（2）/F（2＇） and F（3）/F（3＇））, is disordered over two orientations in an approximate 3：1 ratio.     

Crystal Structures and Characterizations of Bis(pyrrolidinedithiocarbamato)Cu（Ⅱ） and Zn(Ⅱ） Complexes

The structures of [Cu (S₂CN (CH₂)₄)₂] (1) and [Zn₂(S₂CN‐(CH₂)₄)₄] (2) have been determined by X‐ray crystallography analysis. They are all isomorphous and triclinic, space group of P1^?, with Z = 1. The lattice parameters of compound 1 is: a = 0.63483(2) nm, b = 0.74972(3) nm, c=0.78390(1) mn, α = 75.912(2)°, β = 78.634(2)° and γ = 86.845(2)°; compound 2: a = 0.78707(6) nm, b=0.79823(6) nm, c = 1.23246(9) nm, α = 74.813(2)°, β = 73.048(2)° and γ = 88.036(2)°. The copper atom is located on a crystallographic inversion center and zinc atom lies across centers of symmetry. The Cu(II) ion has a square‐planar geometry while Zn(II) has a distorted tetrahedral geometry. The thermal gravity (TG) data indicate that no structural transitions in the two compounds were abserved and the decomposition products can adsorb gas. Also they all have a high thermal stability.     

Syntheses and Crystal Structures of Three Palladium（Ⅱ） Complexes with Isonitrosobenzoylacetoneimine Ligand

Three palladium (II) complexes with the isonitrosobenzoylacetoneimine (HIBI) ligand, Pd (p‐CH₃C₆H₄IBI)₂ (1), Pd (C₆H₅IBI)₂ (2) and Pd₂Cl₂ (C₆H₅CH₂IBI)₂ · CHCl₃ (3), were prepared and characterized by IR, Raman and X‐ray diffraction studies. The geometries around the palladium atoms in the complexes 1 and 2 are distorted trans‐PdN₄ square planes, and the Schiff base ligands RIBI^? are coordinated through their oximo‐nitrogen atoms and imino‐nitrogen atoms. The week Pd…H? C agostic interactions [Pd…H = 0.2764 nm] complete the hexacoordinate environment around palladium in the complex 1. The octahedral deformation of the classical square planar environment of the Pd atom is due to the week Pd…O (1b) interactions [Pd? O (1b) = 0.3157 (9) nm] in the complex 2. The complex 3 is a first example of binuclear complex with isonitrosoketoimine ligands, in which one of oximo groups is coordinated through oximo‐nitrogen and oximo‐oxygen atoms.     

Syntheses and Crystal Structures of One-dimensional Ni（Ⅱ） Complexes with 5-Tert-butyl Isophthalic Acid

Two new Ni（ Ⅱ） coordination polymers, {[Ni（tbip）（bipy）（H2O）]-0.5H2O}n 1 and [Ni（tbip）（phen）（H2O）]n 2 （Hatbip = 5-tert-butyl isophthalic acid, bipy = 2,2＇-bipyridine, phen = 1,10-phenanthroline）, have been synthesized under hydrothermal conditions and characterized by elemental analysis, X-ray diffraction, and IR spectroscopy. In the two polymers, H2tbip acts as a tridentate ligand. Compound 1 has a tbip bridged 1-D linear chain which is extended by hydrogen bonds into a 1-D double chain, while compound 2 exhibits a 1-D zigzag chain.     

Synthesis and Crystal Structure of Two One—dimensional Chain Copper Complexes [Cu（TTA）2（4,4‘’—azpy）] and [Cu（TTA）2（3,3‘’—azpy）

Two copper complexes [Cu(TTA)₂(4,4′‐azpy)] (1) and [Cu‐(TTA)₂(3,3′‐azpy)] (2) (HTTA = 1,1,1‐trifluoro‐3‐(2‐thenoyl)‐acetone, 4,4′‐azpy = 4,4′‐azobispyridine, 3,3′‐azpy = 3,3′‐azobispyridine) were synthesized and characterized. The crystal structures were determined by X‐ray diffraction analysis. The crystal 1 belongs to triclinic with space group P1 , a = 0.8515(2) nm, b = 0.9259(2) nm, c = 0.9468(2) nm, a = 66.126(9)°, β = 79.667(9)°, γ = 90.13(1)°, Z = 1, V = 0.6692(2) nm³, D_c = 3.425 g/cm³, γ = 2.113 mm^?1, F(000) = 694, R₁ = 0.0594, wR₂ = 0.1499. The crystal 2 belongs to monoclinic with space group P2₁/c, a = 1.0661(2) nm, b = 1.4296(3) ran, c = 1.0041(3) nm, β = 114.50(3)°, V = 1.3926(5) nm³, Z = 2, D_c = 1.646 g/ cm³, μ = 1.015 mm^?1, F(000) = 694, R₁, = 0.0535, wR₂ = 0.1113. In the crystals of complexes 1 and 2, the copper atoms have distorted octahedral symmetry. The two compounds possess very similar one‐dimensional linear chains linked through the rodlike 4,4′‐azpy ligands or 3,3′‐azpy ligands.     

Syntheses and Crystal Structures of Lanthanide Complexes of New 15-Membered Macrocyclic Ligands with Three Pendant Acetato Groups

Two new 15-memhored fimctionalized macrocycles, dioxo-polyazacydoalkanes with three pendant acetato groups, have been synthesized by the condensation reaction of DTPA dianhy-dride (DTPA = diethylenetrlamlnepentaacetic acid ) with 1,2-di-amlnopropane, ( 15-DTPA-1, 2-pn), or 1, 2-diaminocydohex-ane, (15-DTPA-1,2-cy). Their lanthanide complexes [ Ln ( 15-DTPA-1,2-pn)(H2O)]2[Ln= Eu (1), Gd (2)] and [Ln(15-DTPA-1,2-cy)(H2O)]2[Ln= Eu (3), Gd (4)] were also pre-pared. Single crystal X-ray diffraction analyses of complexes 2 and 4 show that they have dimeric structures in solid state;each metal ion is nine-coordinated in a distorted tricapped-trig-onal prism. In complex 4, the coexistence of two diastereoiso-meric molecules in the crystal lattice was observed.     

Synthesis and Crystal Structure of Dissymmetrical Double Schiff Base Cu（Ⅱ） Homobinuclear and Cu（Ⅱ）-Mg（Ⅱ）-Cu（Ⅱ） Heterotrinuclear Complexes

Homobinuclear complex （HCuL）2 （1） （H3L： N-3-carboxylsalicylidene-N＇-salicylaldehyde-1,2-diaminoethane） was obtained from self-organization of the reported complex HCuL, and its crystal structure was determined through X-ray diffraction at room temperature. The crystal of complex 1 belongs to monolinic system, the space group Cc, a=2.5326（5） nm, b=0.88861（18） nm, c=1.3738（3） nm, β=96.95（3）°, Z=4, R1=0.0520, wR2=0.1185. （HCuL）2 is a dimeric molecule and has extended phenolic oxygen-bridged structure. In addition, using mononuclear complex HCuL as building blocks, Cu（Ⅱ）-Mg（Ⅱ）-Cu（Ⅱ） heterotrinuclear complex 2 was synthesized, and its crystal structure also has been determined by X-ray analysis. The crystal of complex 2 is of monoclinic system, space group Pc, a=1.1816（2） nm, b=1.5599（3） nm, c=1.9642 （4） nm, β=98.22°, Z=2, R1=0.0701, wR2=0.1498. Each dissymmetricai cell unit of complex 2 contains two heterotrinucler neutral molecules： {[CuL（H2O）]Mg[CuL（CH3OH）]} and {[CuL]Mg[CuL（H2O）]}.     

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.     

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.     

Four New Cu（Ⅱ） Complexes with Benzotriazole-based Ligands： Syntheses,Crystal Structures and Theoretical Investigations

Four new Cu（Ⅱ） complexes with two benzotriazole-based ligands, [Cu2（L^1）2（NO3）2]· 2H2O （1）, [Cu2（L^1）2]·2ClO4·2H2O （2）, [Cu2（HL^2）2（NO3）4]·2CH3COCH3 （3） and [Cu（HL^2）2（Cl）]·Cl·2CH2Cl2 （4）, where HL^1 = 1,3-bis（benzotriazol-2-yl）-2-propanol and HL^2 = 1,3-bis（benzotriazol-1-yl）-2-propanol, were synthesized and structurally characterized by elemental analyses, IR and single-crystal X-ray diffraction analyses. It is revealed that complexes 1～3 have dinuclear structures, while 4 possesses a one-dimensional （1-D） chain structure, which extends in two orthogonal orientations. In 1～4, the coordination numbers of Cu（Ⅱ） centers range from four to six, which may be attributed to the different geometries and coordination abilities of the ligands and anions. The L^1 ligand in complexes 1 and 2 adopts a tridentate di-chelating coordination mode, whereas ligand HL^2 in complexes 3 and 4 has a bidentate bridging coordination mode. The different coordination modes of these two ligands may be explained by the different charges of nitrogen donor atoms in the benzotriazole ring, which has been investigated by density functional theory （DFT） calculations.     

Novel Isatin-Schiff Base Cu （Ⅱ） and Ni（Ⅱ） Complexes. X-ray Crystal Structure of Bis[3-（4-hexylphenylimino）-1H-indol-2（3H）-one]- dichlorocopper（Ⅱ） Complex

Schiff base ligand （HL） derived from 4-hexylaniline with isatin （1H-indole-2,3-dione） and its complexes with Cu（Ⅱ）, Ni（Ⅱ） were prepared and characterized by analytical, spectroscopic （IR, UV-Vis, Mass） techniques, electrical conductivity, magnetic and thermal measurements. The crystal and molecular structure of [Cu（HL）2Cl2] was determined by a single-crystal X-ray diffraction study. The molecular structure of the title compound has an inversion center on the Cu atom.     

Synthesis and Crystal Structure of a Dinuclear Complex of Cu（II） with Tetra（3,5-diphenyl pyrazole）

A Cu(II) complex of tetra(3,5-diphenyl pyrazole) [Cu(C15H12N2)2Cl2]2 (1) was synthesized, and its structure was determined by single-crystal X-ray diffraction and further characterized by elemental analysis, NMR and IR. 1 belongs to the monoclinic system, space group P21/c with a = 13.3780(5), b = 15.1392(6), c = 15.5923(6) , β = 124.522(2)°, Z = 2 and V = 2601.86(17) 3. In 1, each Cu2+ ion is coordinated with two N atoms from two tetra(3,5-diphenyl pyrazole) ligands and three Cl- anions to give a distorted square-pyramidal geometry, which is further linked through edge-sharing bridging by Cl- anions to form a centrosymmetric dinuclear structure.     

Syntheses and Crystal Structures of Ternary Complexes of Zinc（Ⅱ） and Cadmium（Ⅱ） with 3-Aminobenzoic Acid and 1,10-Phenanthroline

1 INTRODUCTION Benzoic acids with substituent of amino are a class of rigid ligands possessing several functional groups. When they coordinate to metal ions, versa- tile coordination modes will be presented with pre- sence of not only coordinate-covalent bonds but also hydrogen bonds. Besides, diverse coordination modes of carboxyl and rigid frame of benzene ring gua- rantee the stability of multi-dimensional structures of the synthesized metal complexes. Thus ligands of this class are o…