Syntheses and Crystal Structures of Hg(Ⅱ)and Ag(Ⅰ)Complexes Containing 2-Acetylpyridine-paminobenzoylhydrazone Ligand

The two complexes [HgI_2L]（DMF）（1） and [AgL_2]（ClO_4）（CH_3CN）（2） were synthesized from the reaction of Schiff base ligand（2-acetylpyridine-p-aminobenzoylhydrazone）（L） with HgI_2 or AgClO_4 respectively. The compounds are characterized by ^1H NMR,FTIR and elemental analysis. The structures of the ligand and two complexes are measured via single-crystal X-ray diffraction. In these two complexes,the structures are both distorted triangular bipyramids with five-coordinated centers.

Syntheses,Crystal Structures and Antibacterial Activities of Schiff Base of Nickel(Ⅱ)and Copper(Ⅱ)Complexes

A new kind of Schiff base HL（HL= 1-phenyl-3-methyl-4-（p-methylbenzoyl）-5-pyrazolone with L-Leucine methyl ester） and complexes Ni L′_2·0.75C_2H_5OH·0.25H_2O,Cu L′′2（L′ = 1-phenyl-3-methyl-4-（p-methylbenzoyl）-5-pyrazolone with L-leucine ethyl,L′′ = 1-phenyl-3-methyl-4-（p-methylbenzoyl）-5-pyrazolone with L-leucine） have been synthesized and structurally determined by X-ray diffraction. For HL： crystal structure determination indicates that there are two independent HLs with different conformations in one asymmetric unit. For complex 1： the Ni（Ⅱ） ion is six-coordinated by two carbonyl oxygen atoms from pyrazolone ring,two nitrogen atoms from different HL′ and two oxygen atoms from L-Leucine ethyl ester to form a distorted octahedral geometry. For complex 2： the Cu（Ⅱ） ion is four-coordinated by one carbonyl oxygen atom from the pyrazolone ring,one nitrogen atom from HL′′,and two different carboxylic oxygen atoms from L-leucine with the same conformation to form a distorted quadrilateral geometry.

Synthesis,Crystal Structure and Fluorescent Properties of Silver and Cadmium Complexes

Two new complexes [Ag（bix）]n·n NAA·n H2O（1） and [Cd（NAA）（phen）2（H2O）]2· 2CH3COO-·H2O（2）（bix = 1,4-bis（imidazol-1-ylmethyl）benzene,HNAA = α-naphthylacetic acid,phen = 1,10-phenanthroline） have been successfully synthesized under hydrothermal conditions.Their structures have been determined by elemental analyses,IR spectroscopy,TG and single-crystal X-ray diffraction analysis.The intermolecular hydrogen bonding or π-π stacking interactions extend the complexes into a 3D supramolecular structure.Moreover,the luminescent properties of complex 2 have been investigated in the solid state.

THE FIRST BINUCLEAR MOLYBDENUM AND TUNGSTEN COMPLEXES WITH DOUBLY-BRIDGING PYRIDINE-2-THIOLATO LIGANDS.X-RAY CRYSTAL STRUCTURE OF THE COMPLEX[Mo_2(CO)_4(μ-pyS)_2(PPh_3)_2].2C_7H_8

The title complex was obtained by reactions of [Mo(CO)_3(MeCN)_3] with [CuBr(pySH)(PPh_3)_2]or directly with pySH and PPh_3. The latter method can be used to synthesize the corresponding tungsten complex [W_2(CO)_4(μ-pyS)_2(PPh_3)_2].The molecular structure of the title compound was determined by X-ray diffraction method.

Hydrothermal Syntheses and Crystal Structures of Two Complexes with 3,5-Dinitrosalicylate and 2,2′-Bipyridine Ligands

The two title complexes, [Cd{3,5-（NO2）2sal}（2,2′-bipy）]n 1 and [Mn{3,5- （NO2）2sal}（2,2′-bipy）]n 2 （3,5-（NO2）2sal = 3,5-dinitrosalicylate, 2,2＇-bipy = 2,2′-bipyridine）, were synthesized by the hydrothermal reaction and structurally characterized. Complex 1 crystallizes in triclinic, space group P1, a = 5.581（4）, b = 12.071（8）, c = 12.88（1）A, α= 92.10（3）,β= 96.73（3）, γ = 102.02（2）°, C17H10N407Cd, Mr = 494.69, V= 841（1）A3, Z = 2, Dc = 1.954 g/cm3, F（000） = 488, μ= 1.353 mm^-1, R = 0.0248 and wR = 0.0761. Complex 2 crystallizes in monoclinic with space group P21/c, a = 8.604（3）, b = 23.88（1）, c = 8.894（3） A, β = 102.45（1）°, C17H10N407Mn, Mr = 437.23, V= 1785（1） A3, Z=.4, Dc = 1.627 g/cm3, F（000） = 884, μ = 0.791 mm^-1, R = 0.0471 and wR = 0.1250. Complex 1 possesses an infinite 1D polymeric chain structure consisting of the repeated basic four-membered ring units （Cd2O2） and eight-membered ring units （CdOCO）2. Compound 2displays a linear 1D chain through Mn（Ⅱ） atoms and bridging carboxylate groups of 3,5-dinitrosalicylic acid ligands with the Mn…Mn separation of 4.472（2）A. The fluorescence properties and cyclic voltammetric behaviors of the complexes are also reported.

SYNTHESES OF TUNGSTEN COMPLEXES WITH o-MERCAP-TOPHENOL.CRYSTAL STRUCTURE OF (Ph_4P)[WO(OMe)(mp)_2]

Reaction of WCl6, mpH2 o-mercaptophenol) and MeONa in the presence of Ph4PBr gave complexes (Ph4P)[W(mp)3] (1) and (Ph4P) CWO(OMe) (mp)2] (2). Crystal data complex (2), C37H31O4PS2W, Mr = 818. 61, monoclinic, space group P2/a, a=26. 555(3), b=9. 634(1), c=13. 523(7) A. β=94. 68 (2)°, V=3448. 1 A3. A=1. 58 g/cm3, Z = 4. λ(MoKα)=0. 71073 A , μ= 36. 2 cm-1, F(000) = 1624, T=296K, final R(Rw) = 0. 068(0. 070) for 3929 observed reflections. The WO4S2 core is arranged in a distorted octahedral geometry.

Investigation on Molecular and Crystal Structures of Metal Complexes with Aminopolycarboxylic Acids(Ⅰ)─Synthesis and Structure of Na_2[Fe~Ⅲ(ida)2]2·3H_2O

The crystal structure of the title complex salt has been determined by single-crystal X-ray structure analysis. The crystal data are as follows; Monoclinic, P21/c, a=15.6480(10)A,b=16.7870(10)A, c=10.347(2)A, β=90.790(10), V=2717.7(6)A3, Z=3, and R=0.0333 for 4789 unique reflections. The complex anion has a pseudo-octahedral structure distorted more than the CrⅢand CoⅢ analogs, in which cach iminodiacetato ligand (ida2-) is coordinated in a facial fashion with the two N atoms in a cis configuration, resulting in an unsyin-fac structure.

ClO_4^--directed Assembly of Two Co^ⅡComplexes Based on Flexible N-donor Ligands:Syntheses,Crystal Structures and Magnetic Properties

The reaction of Co^II ions with 1,4-bis（imidazol）butane（bimb） or 1,4-bis（triazol）butane（bitb） in the presence of ClO4^-, respectively affords two CoII coordination complexes, namely {[Co（bimb）3]·2ClO4}n（I） and {[Co（bitb）3]·2ClO4}n（II）. Single-crystal X-ray analysis indicates that both complexes I and II show the same α-Po topological structures. However, complex I exhibits a 2-fold interpenetrating network, while complex II features a 3-fold interpenetrating network. In addition, solid-state properties such as thermal stabilities and magnetic properties of two complexes were also investigated.

Reactivity of Fe3(CO)(12) with Alkynes R-C≡C-R＇： Syntheses and Crystal Structures of Substituted Cyclic Ketones and Carbonyl Iron Complexes

The reactivity of carbonyl iron cluster with alkynes has been studied by the thermal reaction of Fe_3（CO）_（12） with R-C≡C-R＇（R = Fc（Ferrocenyl）; R′ = Ph（Phenyl）, Fc, H）. The hexacarbonyldiiron cluster with ferracyclopentadiene ring（μ_2, η~4-C_4Ph_4）Fe_2（CO）_6（1） and one tetraphenyl substituted cyclopentadienone（Ph_4C_4CO）（2） were simultaneously obtained by the reaction of Fe_3（CO）_（12） with alkyne（Ph-C≡C-Ph）. Only one ferrole cluster（μ_2, η~4-C_4Fc_2H_2）Fe_2（CO）_6（3） was separated by using Fc-C≡C-H as alkyne. One tri-carbonyl iron complex（η~4-C_4Fc_4CO）Fe（CO）_3（4） and an unexpected new cyclic ketone compound 2,2,4,5-tetraferrocenylcyclopenta-4-en-1,3-di-one [Fc_4C_3（CO）_2]（5） were obtained by using Fc-C≡C-Fc as alkyne. A new complex（η4-2,4-diphenyl-3,5-diferrocenylcyclopenta-2,4-dien-1-one）-tricarbonyl iron（η~4-C_4Ph_2Fc_2CO）Fe（CO）_3（6） was synthesized by the reaction of Fe_3（CO）_（12） with Fc-C≡C-Ph. The structures of compounds 1~6 were determined by X-ray single-crystal diffraction and spectroscopic characterization. The crystal structures of two new compounds 5 and 6 were analyzed. Our experimental results reveal the structural models of the reaction products are affected by the kinds of substituents from alkynes R-C≡C-R′.

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）A, 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） A, β = 111.237（14）°, V = 3017（4） A^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.

Hydrothermal Syntheses and Crystal Structures of Two Complexes with Cyclic Dimer and 2D Network Structures of 3-Nitrophthalate and N-Donor Ligand

Two complexes, [Cd（nphth）（2,2＇-bipy）（H20）]2.2H20 （1） and [Cd（nphth）（4,4＇- bipy）（H20）], （2） （nphth = 3-nitrophthalate, 2,2＇-bipy = 2,2＇-bipyridine, 4,4＇-bipy = 4,4＇-bipyridine）, were synthesized by hydrothermal reactions and structurally characterized. Complex 1 crystallizes in triclinic with space group Pi, a = 0.7599（4）, b = 1.0551（6）, c = 1.2448（6） nm, α = 88.96（2）, β = 75.40（2）, γ= 76.76（2）°, V= 0.9393（9） nm3, Z = 1, Dc = 1.816 Mg/m3, F（000） = 512, μ = 1.217 mm-1, S = 0.946, the final R = 0.0238 and wR = 0.0631, Complex 2 crystallizes in monoclinic, space group P21/c, a = 0.737（5）, b = 2.338（1）, c = 1.0030（6） nm, β = 96：359（9）°, V= 1.803（2） nm3, Z = 4, Dc = 1.826 Mg/m3, F （000） = 984,μ = 1.260 mm-1, S = 1.016, the final R = 0.0455 and wR = 0.1007. Complex 1 exhibits a discrete cyclic binuclear structure and complex 2 possesses a 2D layer structure with cyclic binuclear unit. The fluorescent spectrum study shows that complex 1 exhibits fluorescent emission in the solid state at room temperature.

Organic Melt Crystallization as a Method for Synthesis of Supramolecular Complexes

The most simple method for solventless synthesis of supramolecular complex of CMCR·2BPY·BZP, [CMCR = C-methylcalix[4]resorcinarene, BPY = 4,4'-bipyridine, BZP = benzophenone], is proposed. Although CMCR by itself is high melting point compound (above 300°C), CMCR was found to be dissolved in melt mixture of BPY and BZPeven below 120°C. In the mixture of the three components, the reaction occurs to form CMCR·2BPY·BZP supramolecular complex.

Synthesis, Crystal Structure and Luminescent Property of [Zn(C_(12)H_9O_3)_2(C_(10)H_8N_2)]_n·nH_2O

Under hydrothermal condition, the reaction of 2-naphthoxyacetic acid with ZnCl2 and 4,4′-bipyridine （4,4′-bipy） has afforded a new Zn（Ⅱ） compound, [Zn（C12H9O3）2（C10H8N2）]n·nH2O1, which was structurally characterized by single-crystal X-ray diffraction analysis. The crystal is of monoclinic, space group P21/c with a = 7.7335（2）, b = 19.3834（4）, c = 20.1707（4） A, β = 104.9830（10）°, V = 2920.82（11） A^3, C34H28ZnN2O7, Mr = 641.95, Z = 4, Dc = 1.460 g/cm^3,μ = 0.895 mm^-1, F（000） = 1328, R = 0.0406 and wR = 0.0876 for 4417 observed reflections （I〉 2σ（I）） Complex 1 consists of one-dimensional zigzag chains deriving from Zn（C12H9O3）2 units linked by 4,4′-bipy ligands, and lattice water molecules decorate between the chains. Non-covalent interactions, such as hydrogen-bonding and aromatic π-π interactions, lead to the formation of a 3D network structure. The thermogravimetric analysis （TGA） and luminescent property for 1 have also been studied in this paper.

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,Crystal Structure and Heterogeneous Catalysis of a New Chiral Manganese Coordination Polymer Based on the Schiff-base Ligand

A homochrial manganese（Ⅲ） complex（1） derived from chiral salen ligand（1 R,2 R）-（-）-1,2-diphenylethane-1,2-diamine-N,N？-bicarboxyl-salicylidene） has been synthesized through solvothermal procedure and characterized by IR,elemental analysis,TGA,circular dichroism（CD）,powder and single-crystal X-ray crystallography.It crystallizes in orthorhombic,space group P212121 with a = 9.108（3）,b = 16.431（5）,c = 26.531（6） A,V = 3970.4（19） A^3,Z = 4,Dc = 1.248 g/cm^3,F（000） = 1568,Mr = 745.73,μ = 0.383 mm^-1,the final GOOF = 0.957,R = 0.0631 and wR = 0.1079 for 13250 observed reflections with I 〉 2σ（I）.The coordination polymer 1 possesses a 1 D infinite zigzag chain architecture constructed by the dicarboxyl-functionalized metallosalen ligand（Mn-salen）,and the polymeric chains are further assembled into a 3D supramolecular network structure via strong intermolecular hydrogen bonding interactions between adjacent zigzag chains.As a heterogeneous catalyst,1 was used as an efficient heterogeneous catalyst for the asymmetric olefin epoxidation.

Synthesis,Crystal Structure and Optical and Photocatalytic Properties of a Discrete Cuprous Iodide Compound with a Transition Metal Complex Cation

With transition metal complex, a discrete cuprous iodide compound, namely, [Ni（phen）3]2Cu6I10（1, phen = 1,10-phenanthroline） has been solvothermally synthesized and structurally characterized. Single-crystal X-ray diffraction studies revealed that compound 1 crystallizes in triclinic space group P1（No. 2） with a = 11.2694（2）, b = 12.3699（3）, c = 15.0387（3） ？, α = 102.840（2）, β = 105.215（2）, γ = 96.388（2）°, V = 1940.04（7） ^3, Z = 1, Dc = 2.438 g·cm^-3, F（000） = 1324, R = 0.0256 and w R = 0.0555（I 〉 2σ（I））. Compound 1 features a discrete anionic moiety of [Cu6I10]^4- charge-balanced by two metal complexes of [Ni（phen）3]2＋. The optical absorption edge of compound 1 was estimated to be 2.24 eV. Interestingly, nearly 95% of contaminant（crystal violet aqueous solution（CV）, 50 m L, 1.0 × 10^-5 M） could be decolorized after exposure to visible light within 30 min, illustrating an impressive photocatalytic activity of compound 1. The thermal stability of 1 has also been studied.

Synthesis, Crystal Structure and Luminescence Property of a Cd(Ⅱ) Complex Assembled by 4-Carboxymethoxy Phenylacetic Acid

A new structure with the molecular formula [CdL]n was formed by CdSO4 with 4-carboxymethoxy phenylacetic acid （H2L） through the hydrothermal method. The complex was characterized by elemental analysis and infrared spectroscopy. The structure of the complex was determined by single-crystal X-ray diffraction, which is of monoclinic system, space group P21/c with a = 10.3887（2）, b = 7.10710（10）, c = 14.7212（2） , β = 120.6940（10）°, V = 934.65（3） 3, Dc = 2.278 g·cm-3, Z = 4, F（000） = 624, S = 1.022, the final R = 0.0187 and wR = 0.0487 for 2000 observer reflections （Ⅰ 〉 2σ（Ⅰ））. The center metal ion Cd（Ⅱ） in the complex is six-coordinated in a distorted octahedral geometry, and is connected with L ligands to form a 3D fishing net structure, which is a novel （3,6） network topology. The luminescence of the complex has been investigated, and the result reveals that it displays luminescent property in the voilet region.

Synthesis, Crystal Structure and Fluorescent Property of a Zn(Ⅱ) Complex with 1,3-Bis(imidazol-1-yl)benzene and 1,3-Benzenedicarboxylate

A novel zinc complex [Zn（BIB）（bdc）]n（1, BIB = 1,3-bis（imidazol-1-yl）benzene, bdc = 1,3-benzenedicarboxylate） has been synthesized in solvothermal conditions. The title complex was characterized by elemental analysis, IR spectra, thermal analysis, single-crystal and powder X-ray diffraction. The result proved that the alliance of BIB and aromatic carboxylic acids is good for the diversity of getatable structure. Complex 1 crystallizes in the monoclinic system of P2/c space group with a = 11.5591（10）, b = 9.6239（8）, c = 33.727（3）A, β = 103.816（3）°, V = 3643.4（5） A^3, Z = 8, μ = 1.385 mm^-1, F（000） = 1792, Dc = 1.603 g/cm^3 and Mr = 439.72 g/mol. Additionally, luminescent properties of complex 1 are also investigated and it shows good fluorescence.

Synthesis,Crystal Structure and Catalytic Performance of the Trifluoro-substituted Mono(β-diiminato)Copper(Ⅱ)Complex

Two novel copper complexes with methyl or trifluoro-substituted mono-β-diiminato ligands and one acetoxyl anion were synthesized and characterized by IR spectroscopy and elemental analysis for the first time. The structure of complex 2 bearing trifluoro substituents was further confirmed by single-crystal X-ray diffraction. The crystal belongs to the triclinic system, space group P1 with a = 7.377（4）, b = 11.727（6）, c = 12.913（7） ？, α = 116.569（6）, β = 98.829（7）, γ = 96.520（6）°, V = 966.2（8） ？3, Z = 2, Mr = 479.86, Dc = 1.649 g/cm3, F（000） = 482, μ = 1.205 mm-1, the final R = 0.0370 and w R = 0.0903 for 3430 observed reflections with I 〉 2σ（I）. These mono-β-diiminato copper complexes can effectively catalyze methacrylate（MA） polymerization when activated by MMAO. The introduction of fluoro groups into the N-aryl ring of β-diiminato ligands can greatly increase the catalytic activity of copper complexes as well as the molecular weight of PMA.