Syntheses and Crystal Structures of Calix[4]arene Dithiocarbazate Schiff Bases

The regioselective syntheses of novel p-tert-butylcalix[4]arenes with functional aldehyde and dithiocarbazate Schiff base groups were carried out. p-tert-Butylcalix[4]arene was alkylated with o-, p-（ω-chloroalkoxy）- benzaldehydes in the system of K2CO3/KI/CH3CN to give calixarene 1,3-dialdehydes. Then the condensation reactions of active calixarene aldehydes with S-methyl and S-benzyldithiocarbazate, calixarene sulfur-containing Schiff bases were efficiently obtained in satisfied yields. The single crystal analysis of the four representative products shows that calixarene aldehydes and Schiff bases exist in cone conformation and there are interesting intermolecular hydrogen-bands and π...π interaction in the crystals.

Syntheses,Crystal Structures and Kinetic Mechanisms of Thermal Decomposition of Rare Earth Complexes with Schiff Base Derived from o-Vanillin and p-Toluidine

Three complexes, [Pr（NO3）3（HL）2] （1）, [Nd（NO3）3（HL）2] （2） and [Er（NO3）3（HL）2] ·0.5H2O （3）, were synthesized from the reaction of a Schiff base ligand 2-[ （4-methylphenylimino）methyl ]-6-methoxyphenol （C15 H15 NO2, HL） with Ln（NO3）3·6H2O （Ln = Pr, Nd, Er）. Characterization by single-crystal X-ray diffraction technique, elemental analysis, molar conductance, FT-IR, UV-Vis, ^1H NMR and thermal analysis shows the title complexes are neutral molecules where the central Ln（ Ⅲ） ion is ten-coordinated in biapical anti-hexahedron prism geometry, with four oxygen atoms of the phenolic hydroxy and methoxy groups in the two bidentate Schiff base ligands and six oxygen atoms provided by the three bidentate NO3 - anions. Additionally, the kinetic mechanism of thermal decomposition of complex 3 was determined with a TG-DTG curves by both integral and differential methods. The functions of thermal decomposition reaction mechanism and the equation of kinetic compensation effect were obtained.

Synthesis and Crystal Structure of a Zinc(II) Complex Salt with the Schiff Base of Picolinaldehyde N-oxide and Semicarbazone

The title zinc（Ⅱ） complex salt [Zn（H2O）6]（ClO4）2-（PNOS）4, where PNOS is derived from picolinaldehyde N-oxide with semicarbazone, has been prepared and structurally characterized by X-ray single-crystal analysis. It crystallizes in triclinic, space group PI with a = 7.529（3）, b = 10.206（4）, c = 14.678（6）A, a = 86.293（6）, β= 87.686（7）, γ= 81.382（6）°, C28H44Cl2N16O22Zn, Mr = 1093.06, V = 1112.3（8） ,A^3 Z = 1, Dc = 1.632 g/cm^3, S = 1.089, μ（MoKa） = 0.773 mm^-1, F（000） = 564, the final R = 0.0438 and wR = 0.1076 for 3888 independent reflections with Rint = 0.0224. The crystal structure possesses a [Zn（H2O）6]^2＋ cation, two ClO4^- anions and four PNOSs. In the crystal structure, Zn^2＋ cation is located at the symcenter and coordinated by six water molecules. In [Zn（H2O）6]^2＋, an elongate octahedral complex cation, the average Zn-O bond length is 2.087（2） A. There exist a lot of H bonds in the structure, linking the cation [Zn（H2O）6]^2＋, anion ClO4^- and PNOS to form a 3D network.

Syntheses, Crystal Structures and Antibacterial Activities of Schiff Base Ligand and Its Nickel(Ⅱ) Complex

A complex [NIL2] was synthesized, in which L, or to be exact, a Schiff base ligand （HL）, was derived from the condensation of 1-phenyl-3-methyl-4-phenylacetyl-5-pyrazolone （PMPAP） with L-phenylalanine methyl ester. They were characterized by IR and single-crystal X-ray diffraction. Green block crystals of both ligand and its complex were grown at room temperature. The ligand, which consists of two individual fragments, crystalizes in the P1 space group （a = 5.6268（5）, b = 10.6892（11） and c = 19.4869（18） A）. The complex crystalizes in the P21 space group （a -- 21.4076（18）, b = 9.4792（8） and c = 25.287（2） A）, which consists of a nickel six-coordinated compound. Every fragment is a distorted octahedron with four oxygen and two nitrogen atoms. The Schiff base ligand （HL） and its complex have been tested in vitro to evaluate their antibacterial activity against bacteria Escherichia Coli and Bacillus subtilis. It is found that the complex has higher activity than the corresponding free Schiff base ligand （HL） against the same bacterial.

Syntheses, Characterizations, Crystal Structures and Antibacterial Activities of Two Zinc(II) Complexes with a Schiff Base Derived from o-Vanillin and p-Toluidine

Two new zinc（Ⅱ） complexes, [Zn2L2Ch].2[ZnL（CH3OH）Cl2] 1 and [ZnL2（NO3）2] 2, were synthesized by reacting ZnX2.nH2O （X = Cl^-, NO3^-） and a Schiff base ligand 2-[（4-methylphenylimino）methyl]-6-methoxyphenol （C15HIsNO2, L） which was obtained by the condensation of o-vanillin （2-hydroxy-3-methoxybenzaldehyde） with p-toluidine. Both 1 and 2 were characterized by single-crystal X-ray diffraction technique, elemental analysis, molar conductance, FT-IR, UV-Vis, IH-NMR spectra and thermogravimetrie analysis. The Schiff base ligand and its zinc（Ⅱ） complexes have been tested in vitro to evaluate their antibacterial activity against bacteria, viz., Escherichia Coli, Staphylococcus aureus and Bacillus Subtilis. The results show that these complexes have higher activity than the corresponding free Schiff base ligand against the same bacteria.

Synthesis and Crystal Structure of a New Three-dimensional Supramolecule of Copper(Ⅱ) Schiff Base Complex

A new three-dimensional supramolecule composed of copper-Schiff base complex, [Cu（naphdien）]Cl·H2O, where naphdien is Schiff base of 2-hydroxy-1-naphthaldehyde and diethylenetriamine, has been synthesized and determined by single-crystal X-ray diffraction. It belongs to the monoclinic system, space group P21/c, with a = 7.3490（15）, b = 7.0847（16）, c = 30.845（3）A, β= 95.33（3）°, V = 1599.0（5）A3, Z = 4, C15 H20ClCuN3O2, Mr = 373.33, De = 1.551 g/cm3, μ = 1.543 mm^-1, F（000） = 772, R = 0.0536 and wR = 0.0927 for 2788 unique reflections with 1659 observed ones （I 〉2σ（I））. In the crystal structure, mononuclear units [Cu（naphdien）]Cl·H2O are linked into a two-dimensional framework via strong hydrogen bonds, and extended into a three-dimensional supramolecular structure through π-π stacking interactions.

Synthesis, Crystal Structure and Cytotoxic Activity of a Novel Nickel(II) Complex with Schiff Base Derived from Salicylhydrazide

A novel Schiff base complex with π-conjugated system, [Ni（L1）2（py）2] 1 （L1 =（E）-N′-（2,4-dichlorobenzylidene）-2-oxidobenzohydraizide）, was synthesized and characterized by elemental analysis and single-crystal X-ray determination. Complex 1 crystallizes in the monoclinic system, space group P21/n with a = 12.8286（10）, b = 16.3573（13）, c = 19.0206（14） A, β = 108.2920（10）°, V = 3789.6（5）A^3, Z = 4, Mr = 833.17, Dc = 1.460 g/cm^3,/t = 0.843 mm^-1, F（000） = 1704, the final R = 0.0537 and wR = 0.0640 for 3836 observed reflections with I 〉 2σ（I）. In the molecular structure of 1, the Ni^Ⅱ atoms are six-coordinated by two N and two O atoms from two Schiff base ligands （LI） and two N atoms from two pyridine solvent molecules to form a distorted octahedral geometry. The cytotoxic activities of complex 1 have been experimentally studied against a human HeLa cell in vitro.

Synthesis and Crystal Structure of a Novel Binuclear Cu(Ⅱ) Complex with Tetradentate Schiff-base Ligand

A novel binuclear complex （[Cu^2（μ2-shed）（hshed）].（CIO4）,H2O, h2shed = N-salicylidene-N＇-（2-hydroxyethyl）ethylenediamine） has been synthesized and structurally characterized by X-ray diffraction analysis. It crystallizes in monoclinic, space group P21/c with a = 12.511（10）, b = 15.750（12）, c = 14.281 （12） A, β = 100.564（14）°, C22H31CIN4O9Cu2, Mr = 658.04, V = 2766（4） A^3, Z = 4, Dc = 1.580 g/cm^3,μ（MoKα = 1.689 mm^-1, F（000） = 1352, the final R = 0.0528 and wR = 0.1433 for 4880 independent reflections with Rint = 0.0577. The complex is a binuclear copper compound, and two Cu（Ⅱ） ions in the binuclear cation are in different coordination environments. The Cu（1） ion adopts a distorted square pyramidal geometry （x = 0.22） with four donor atoms （N2O2） of the ligand in the basal plane, and one hydroxyl oxygen atom with protonated form occupying the apical position. The Cu（2） ion assumes the geometry of a distorted square plane with four donor atoms （N2O2） of the ligand. The Cu...Cu separation is 3.103 A,. In addition, N-H…O and C-H…O intermolecular hydrogen bonding interactions link these binuclear cations into a quasi one-dimensional chain along the a axis.

Synthesis and Crystal Structure of Complex of Zinc(Ⅱ) with Schiff Base {Zn[CH_3O(O)-C_6H_3CH_3=NN=C(S)NH_2](DMF)}_2

The title complex is a new binuclear Zn(Ⅱ) with chelate ligand of Schiff base containing S and N atom.The complex crystallizes in the orthorhombicspace group Pccn,with a=12.338(9),b=16.666(8),c=17.503(6),V=3599(6),Mr=723.52,Z=4,Dx=1.34 g/cm3,μ=15.22 cm-1,F(000)=1488.The structure was solved by direct methods and the final R=0.078.The crystal consists of discrete molecules with symmetric center at the center of the fourmembered ring consisting of two Zn atoms and two O atoms.

Syntheses, Crystal Structures and Antibacterial Activities of Two Heterocyclic Schiff Base Compounds

Two heterocyclic Schiff bases were synthesized via the condensation reactions of primary amines with carbonyl compounds. 2-[（4-pyridylmethylene）-amino] phenol （compound 1） was synthesized by the interaction of 4-pyridinecarboxaldehyde with o-aminophenol in ethanol solvent; N,N＇-bis（3-（furan-2-yl）allylidene）benzene-1,4-diamin （compound 2） was synthesized by the interaction of 3-（2-furyl）acrolein with p-phenylenediamine in ethanol medium. The compounds were characterized by elemental analysis, IR, MS and single-crystal X-ray diffraction. Compound 1 （C12H10N2O） crystallizes in the monoclinic system, space group P21/c with α = 7.0771（7）, b = 7.2820（7）, c = 19.849（2）, b = 96.3390（10）°, V = 1016.66（17） ？3, Z = 4, Mr = 198.22, Dc = 1.295 g/cm3, F（000） = 416, GOOF = 1.060, m = 0.085 mm-1, the final R = 0.0371 and wR = 0.0929 for 1497 observed reflections with I 〉 2σ（I）. Compound 2 （C20H16N2O2） crystallizes in the orthorhombic system, space group Fdd2 with α = 26.344（15）, b = 48.50（3）, c = 5.293（3）, V = 6764（7） ？3, Z = 16, Mr = 316.35, Dc = 1.243 g/cm3, F（000） = 2656, GOOF = 1.043, m = 0.081 mm-1, the final R = 0.0526 and wR = 0.1267 for 2059 observed reflections with I 〉 2σ（I）. 1 and 2 molecules are connected through hydrogen bonds to generate a 2D network and a 1D chain structure, respectively. The preliminary antibacterial activity results showed that the title compounds display excellent antibacterial activities to Escherichia coli, Staphylococcus aureus and Bacillus subtilis.

Synthesis and Crystal Structure of an Azide Bridged Binuclear Zinc(Ⅱ) Dimer Containing Taurine Schiff Base [Zn_2(C_8H_9N_2O_3S)_2·(N_3)_2·(H_2O)_2]_2·_2H_2O

The title complex [Zn2L2（N3）2（H2O）2]·2H2O （L = N-（2-pyridylmethylidene） taurine） has been synthesized in a methanol-water solution. The crystal belongs to monoclinic, space group P2 1/C with a = 15.8064（10）, b = 10.5015（5）, c = 17.3193（11） ,A, β= 111.314（2）°, V = 2678.2 （3） ,A ^3 C16H26N10O10S2Zn2, Mr = 713.33, Z = 4, DC = 1.769 g/cm^3, μ = 2.017 mm^-1 and F（000） = 1456. The asymmetric unit consists of two half-molecules of the complex and two water molecules. Four N and two O atoms form the coordination environment of each Zn atom, resulting in a distorted octahedral configuration. The two halves of each independent dimer are related by a crystallographic inversion centre, which lies at the centre of the ring formed by two Zn atoms and the coordinating atoms of the two azide anions. The average separation of Zn（Ⅱ）...Zn（Ⅱ） is 3.322 A. The molecules are linked by O-H...O hydrogen bonds, generating an interesting zigzag infinite chain structure in the ac plane.

Synthesis,Crystal Structure and Quantum Chemical Investigation of Bis-Schiff Base Compounds Derived from2-phenyl-1,2,3-triazole-4-carboxaldehyde with Diamine

Two new schiff base N,N＇-bis（（2-phenyl-2H-1,2,3-triazol-4-yl）methylene）-1,3-propanediamine （1） and N,N＇-bis（（2-phenyl-2H-1,2,3-triazol-4-yl）methylene） -1,4-butanediamine （2） were synthesized by condensation of 2-phenyl-1,2,3-triazole-4-carboxaldehyde with diamine, and characterized by elemental analysis, IR, IH NMR and MS spectra. Their crystal structures were determined by X-ray single crystal diffraction. Both crystals belong to the monoclinic system, space group P21/c. For compound 1（C21H20N8, Mr=384.45）： a = 16.314（3）, b =5.7168（11）, c = 21.316（4） A, β = 105.3（2）°, Z = 4, V = 1917.6（7） A^3, De =1.332 g/cm^3, F（000） = 808,μ = 0.086 mm 1, R = 0.0533 and wR = 0.1460; for compound 2 （C22H22N8, Mr=398.48）： a = 8.6156（17）, b = 5.2964（11）, c = 22.665（5）A, β = 100.54（3）°, Z = 2, V = 1016.8（4） A^3, De= 1.302 g/cm^3, F （000） = 420, μ = 0.083 mm^-1, R = 0.0373 and wR = 0.1155. Based on the crystal data, quantum chemistry calculation was performed on the two title compounds by means of Gaussian 98 program. The molecular orbital energies and atomic net charges population were obtained. Furthermore, we antilyzed their active atoms. The investigation can serve as a theoretical guide to study the synthesis and activity of the title compounds.

Synthesis, Crystal Structure and Photoluminescence of a 2D Two-fold Interpenetrating Cd(II) Coordination Polymer Based on a Flexible Reduced Schiff Base Ligand

By the reaction of cadmium chloride with a reduced Schiff base ligand （H2L= N-（4- carboxybenzyl）-glycine）, a novel Cd（Ⅱ） compound [Cd（HL）2]·4H2O （1） has been obtained. Single-crystal X-ray diffraction analysis reveals that it crystallizes in orthorhombic, space group Pbcn with a = 13.9788（8）, b = 24.4204（14）, c = 13.9580（8） A, V= 4764.8（5） A^3, Z = 8, Mr = 600.84, Dc = 1.675 g/cm^3,/z = 0.983 mm^-1, F（000） = 2448, S = 1.084, R = 0.0806 and wR = 0.1705 （I〉 2a（1））. It displays a 2D two-fold interpenetrating structure. The Cd（Ⅱ） ions are six-coordinated. The cross-linkage of Cd（Ⅱ） ions by the bridge of HL anions results in a [Cd（HL）2] layer. Every two [Cd（HL）2]n layers are penetrated with each other, resulting in a two-fold interpenetrating double-layer structure by π-π stacking interactions and hydrogen bonds. Such double-layers are further linked by hydrogen bonds into a supramolecular structure. Photoluminescent investigation shows that compound 1 displays strong emission in the purple region.

Synthesis,Crystal Structure and Electrochemistry Properties of a Cobalt(Ⅱ) Complex Based on Asymmetry Schiff Base Ligand

A new cobalt（II） complex [Co（NO2-salen）2]·1.5H2O containing mono acetalization Schiff base ligand（NO2-salen = N-5-nitro-salicylideneamino ethanato） has been prepared through one-pot template condensation, and has been structurally characterized by elemental analysis, IR spectra and X-ray diffraction. It is formulated as C18H23CoN6O7.5, crystallizes in the hexagonal system, space group of R-3c with α = 25.895（18）, b = 25.895（18）, c = 35.075（6）, γ = 120o, V = 20368（3） and Z = 36. The ligand of 5-nitrosalicylaldehyde-ethylene-diamine takes unusual mono asymmetry mode. The Co（II） ion exhibits a coordination number of six, and assumes a distorted octahedral geometry with a N2O4 donor set. The neutral monomeric units of [Co（NO2-salen）2]·1.5H2O are linked into a one-dimensional（1D） structure via the intermolecular hydrogen bonds and weak π-π stacking interactions. Cyclic-voltammetry measurement reveals the oxidation and reduction processes for the complex are irreversible in nature.

Synthesis and Crystal Structure of a Salicylaldehyde Ethylene Diamine Schiff Base Manganese (Ⅲ) Complex

The title compound, [Mn(salen)(salicyl)]?.5H2O ( H2salen = N, N?ethylenebis- (salicylideneaminato), Hsalicyl = salicylaldehyde), has been obtained from the reaction system containing (o-HOC6H4CH=NCH2)2, o-HOC6H4CHO and Mn(ClO4)2?H2O in EtOH solvent and structurally characterized. It crystallizes in the monoclinic, space group P21/c with a = 13.0548(4), b = 13.9254(4), c = 11.6630(1) ? b = 105.199(2)? V = 2046.09(9) ?, Z = 4, C23H22MnN2O5.5, Mr = 469.37, Dc = 1.524 g/cm3, F(000) = 972, m = 0.687mm-1 . R = 0.0630 and wR = 0.1142 for 1901 observed reflections with I >2(I). The Mn(Ⅲ) is coordinated by N(1), N(2), O(1) and O(2) of the Schiff base ligand and phenolate O atom of salicylaldehyde with O(3)Mn distance of 2.050(4) , forming a relatively rare five-coordinate square-pyramidal structure.

Synthesis and Crystal Structure of a Dinuclear Cu(II) Complex with Tridentate Schiff Base and Azido Bridge

A new dinuclear copper(II) complex ([Cu(C12H17N2O)(N3)]2, C24H34Cu2N10O2) has been synthesized and characterized by X-ray structure determination. It crystallizes in the monoclinic system, space group P21/c with a = 18.529(4), b = 10.933(2), c = 14.534(3) ?, β = 111.07(3)°, V = 2748(1) ?3, Z = 4, Mr = 621.69, F(000) = 1288, Dc = 1.503 g/cm3 and μ(MoKα) = 1.590 mm?1. The structure was refined to R = 0.0647 and wR = 0.1846 for 4406 observed reflections (I > 2σ(I)). The asymmetric unit comprises two halfmolecules. The complex is a centrosymmetric dimmer in which the copper atoms are penta-coordinated by three coordination atoms from the corresponding tridentate Schiff base ligand and two bridging azide anions. The Cu(II)…Cu(II) average distance is 3.350(1) ?.

Synthesis and Crystal Structure of a New Nickel(II) Complex with Unsymmetric Quadridentate Schiff Base Containing Oxime

The title complex, C18H15N3NiO3, has been prepared and characterized by X-ray diffraction analysis. It crystallizes in the monoclinic system, space group Cc with a = 10.939(2), b = 22.909(5), c = 6.907(1) ?, β = 116.75(3)°, V = 1545.7(5) ?, Z = 4, Mr = 380.04, F(000) = 784, Dc = 1.633 g/cm3 and μ(MoKα) = 1.279 mm–1. The structure was refined to R = 0.0472 and wR = 0.0893 for 2571 observed reflections with I > 2σ(I). The absolute structure Flack parameter X is 0.01(2). In this crystal structure, strong face-to-face π-π stacking interactions between adjacent molecules lead to a one-dimensional chain structure.

Synthesis and Crystal Structure of a Co(II) Complex with Schiff Base and Imidazole Ligand

The title compound, [Co（C3H4N2）2（C22H18N2O4）]·5H2O （Mr = 659.56）, has been prepared and its crystal structure was determined by X-ray diffraction method. The crystal belongs to monoclinic, space group P21/n, a = 9.6808（2）, b = 26.7204（5）, c = 12.7993（3） A, β = 100.9340（10）°, V= 3250.75（12） A^3, Z = 4, Dc = 1.348 g/cm^3,μ = 0.586 mm^-1, F（000） = 1380, S = 1.131, R = 0.0689 and wR = 0.1883 for 4782 observed reflections （Ⅰ 〉 2σ（Ⅰ））. The title crystal consists of Co（Ⅱ） complex and lattice water molecules. The Co（Ⅱ） complex assumes a distorted octahedral coordination geometry, formed by one Schiff base dianion phenylenediamine-3-methoxysali-cylaldehyde and two imidazole ligands. The π-π stacking interaction occurs between nearly parallel benzene rings of the neighboring complexes.

Crystal Structure and Sensitive Response toward Al^3＋ of the Furaldehyde Schiff Base

A furaldehyde Schiff base, 4-[（2-furanylmethylene）amino]phenol（FMAP）, was synthesized and fully characterized by elemental analysis, ^1H-NMR, IR, MS, UV-Vis, fluorescence and single-crystal X-ray diffraction. It crystallizes in the monoclinic system, space group P2_1/n with a = 6.2566（6）, b = 13.2273（11）, c = 11.3056（9） A, β = 93.1800（10）o, V = 934.19（14） A^3, Z = 4, M_r = 187.19, D_c = 1.331 g/cm^3, λ = 0.71073 a, F（000） = 392, GOOF = 1.022, R = 0.0396 and wR = 0.0992 for 4569 observed reflections with I 〉 2σ（I）. Fluorescent spectroscopic investigation revealed that the Schiff base exhibited a high selectivity and sensitivity toward Al^3＋ over other common metal ions in ethanol solution, and the detection limit of Al^3＋ is up to 1.2 × 10^-7 M. The mass spectra and Job＇s plot analysis confirm the 1：1 stoichiometry between FMAP and Al^3＋.

Syntheses and Crystal Structures of Two VO(IV) Schiff Base Complexes with Oxyammonia Ligand

Two novel VO(IV) Schiff base complexes, VO(SALHA)2[SALHA: salicyaldehyde- oxyammonia] and VO(o-VANHA)2 [o-VANHA: o-vanillin-oxyammonia], have been synthesized with salicyaldehyde or o-vanilline, hydroxylammonium chloride and vanadyl sulfate in absolute methanol, and their crystal structures were determined by single-crystal X-ray diffraction. The vanadium(IV) centers in both complexes are five-coordinate in a distorted square pyramidal geometry. VO(SALHA)2 (C14H12N2O5V, Mr = 339.20) crystallizes in the monoclinic system, space group P21/n with a = 14.716(9), b = 7.175(5), c = 14.716(9) ? b = 113.130(7), V = 1428.8(15) 3, Z = 4, Dc = 1.577 g/cm3, l = 0.71073 ? m(MoKa) = 0.720 mm-1, F(000) = 692, the final R = 0.0466 and wR = 0.0829 for 1561 observed reflections (I > 2s(I)). VO(o-VANHA)2 (C16H16N2O7V, Mr = 399.25) is of monoclinic, space group P21/n with a = 11.386(12), b = 10.405(10), c = 14.627(15) , b = 93.654(19), V = 1729(3) 3, Z = 4, Dc = 1.533 g/cm3, l = 0.71073 , m(MoKa) = 0.615 mm-1, F(000) = 820, the final R = 0.0513 and wR = 0.1129 for 1235 observed reflections (I > 2s(I)).