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

Modified α and β bis(salicylaldoxime)copper(Ⅱ) have been obtained by recrystallization from ethyl acetate(CCDC Nos. 212157 & 212158). The X-ray analysis reveals that the two modificated forms have the same structure with different geometric parameters. The α form crystallizes in the P2(1)/c space group and the β form in the P1 space group. Both the crystal structures consist of centrosymmetric monomeric molecules of Cu(OC_6H_4CNOH)_2. The IR spectra are in agreement with the structural data.

Synthesis and Crystal Structure of Binuclear Copper (Ⅱ) Complex Containing (Dimethylaminomethyl)ferrocene

A binuclear complex including ferrocenyl, Cu2{Fe(C5H5)[C5H4CH2N(CH3)2]}2 (CH3COO)4, was synthesized and characterized by X-ray diffraction. The title complex crystallizes in triclinic, space group P with a = 8.2779(8), b = 9.4830(8), c = 12.262(1) ? = 81.079(5), b = 80.620(4), g = 78.960(4), V = 924.4(1) 3, Z = 1, C34H46Cu2Fe2N2O8, Mr = 849.51, Dc = 1.526 g/cm3, l(MoK) = 0.71073 ? ?= 1.954 mm-1, F(000) = 438, R = 0.0297 and wR = 0.0901. Both cyclopentadienyl rings in each dmaf (dmaf = (dimethylaminomethyl)ferrocene, Fe(C5H5)- [C5H4CH2N(CH3)2]) have an eclipsed conformation. The binuclear molecule has a crystallographic centrosymmetry; four acetates and two Cu atoms form a cage structure with the distance between two neighboring Cu atoms of 2.655(1) .

Syntheses and Crystal Structures of Mono-and Binuclear Copper(Ⅱ) Mixed-ligand Complexes Involving Schiff Base

The mononuclear copper（Ⅱ） complex [Cu（L）（2-AP）] 1 and binuclear copper（Ⅱ） complex [Cu（L）（py）]2 2 （L = C10H11O5NS, taurine o-vanillin, py = prydine, 2-AP = 2-aminopyridine） with mixed ligand have been synthesized and characterized by X-ray diffraction method. Crystal data for 1： orthorhombic, space group Pbca with a = 11.921（4）, b = 15.816（6）, c = 17.076（6） A, V= 3219.7（19） A^3, C15H17CuN3O5S, Z = 8, Mr = 414.92, De = 1.712 g/cm^3,μ（MoKα） = 1.520 mm^-1, F（000） = 1704, the final R = 0.0300 and wR = 0.0705 for 2840 observed reflections with I 〉 2σ（I）; and crystal data for 2： monoclinic, space group P21/c with a = 7.929（3）, b = 17.038（5）, c = 11.734（4） A, β = 98.162（6）°, V = 1569.1（9） A^3, C15H16CuN2O5S, Z = 4, Mr = 399.90, Dc = 1.693 g/cm^3, F（000） = 820,μ（MoKα） = 1.554 mm^-1, the final R = 0.0351 and wR = 0.0848 for 2767 observed reflections （I 〉 2σ（I））. The molecular structure of complex 1 consists of one tetra-coordinated Cu（Ⅱ） atom generating a slightly distorted square plane, and a one-dimensional chain structure is formed by intermolecular hydrogen bonds. Complex 2 consists of a diphenolic hydroxyl O-bridged binuclear copper（Ⅱ） structure. The crystal structures of complexes 1 and 2 reveal that the coordinate copper centers are bound to both nitrogen and oxygen atom donors. The usual N,O-trans arrangement of ligands is observed in both cases.

Synthesis and Crystal Structure of 1-D Chain Copper(Ⅱ) Complex: [Cu(L)Cl_2]_n (L=2,5-Di-2-pyridyl-1,3,4-oxodiazole)

The title complex, [Cu(L)Cl2]n (L = 2,5-di-2-pyridyl-1,3,4-oxodiazole) 1, has been obtained from the reaction of 3,6-di-2-pyridyl-1,2,4,5-tetrazine (bptz) and CuCl2?H2O in a mixture solvent of CH3CN and CH2Cl2 (L is generated from the metal-assisted hydrolysis reaction of bptz) and structurally characterized. It crystallizes in space group C2/c of monoclinic system with cell parameters: a = 9.812(2), b = 12.679(3), c = 11.111(2) ? b = 103.92(3)? V = 1341.6(5) 3, Z = 4, Dc = 1.776 g/cm3, Mr = 358.66, F(000) = 716, ?= 2.024 mm1 and S = 1.004. The final R = 0.0346 and wR = 0.0938 for 1011 observed reflections with I > 2(I). The Cu(Ⅱ) ion is six-coordinated by four N atoms of two L ligands and two Cl ions in a distorted octahedral geometry. The ligand L acts as a bis-bidentate ligand to bridge the Cu(Ⅱ) ions, resulting in an infinite chain structure.

Hydrothermal Synthesis and Crystal Structure of Binuclear Copper(Ⅱ) Complex Bridged by 1,2,4,5- Benzenetetracarboxylato Trivalent Anion

The title complex [(phen) 2Cu(Htcb)Cu(phen) 2]H 3tcb(tcb=1,2,4,5-benzenetetracarboxylato tetravalent anion; phen=1,10-phenanthroline) was synthesized by the hydrothermal synthesis method. The crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in the triclinic system with space group P1, a=1.04174(8) nm, b=1.07119(8) nm, c=1.26360(10) nm, α=98.169(2)°, β=99.679(10)°, γ=93.658(10)°, V=1.37031(18) nm3, Z=1. The two copper(Ⅱ) cations are bridged by Htcb in the monodentate fashion, and have the same five-coordinated environment completed by the four N atoms from the two phen molecules and one O atom from the carboxylic group of Htcb respectively, which can be best described as distorted trigonal-bipyramid geometry. Moreover, the three dimensional network is formed by H-bonding interactions [O…O distance from 0.2506(10) nm to 0.3176(11) nm] and π-π stacking interactions between the phen rings of adjacent binuclear entities with a face-to-face separation of ca. 0.354 nm.

X-ray Crystal Structure of a Mononuclear Copper (Ⅱ) Complex with Unusual Monodentate O-coordination of Carboxylate Group of Isonicotinate

Reaction of Cu(ClO4)2'6H2O with tripodal ligand tri s (2-benzi nd dazol yl methyl ) aInine(ntb) and sodium isonicotinate (Iso) yielded a mononuclear complex lCu(ntb)(lso)]ClO4.3.5H2O. Thestructure has been established by X-ray crystallography The Cu (Ⅱ) atom is in a distorted trigonalbipyranddal environment with three benzimindazole N atoms of ntb defining the equatorial plane, oneandne N atom of ntb, and one O atom of the carboxylate group of isonicotinate occupying the axialpositions.

Synthesis and Crystal Structure of Bis(barbiturato)triwater Complex of Copper(Ⅱ)

The crystal structure of the bis(barbiturato)triwater copper(Ⅱ) complex formulated as Cu(barb)2(HO2)3 (barb = barbiturato) has been determined by single-crystal X-ray diffraction. The analysis was carried out by direct and Fourier methods and the structure was refined by full-matrix least-square computations. The title compound crystallizes in orthorhombic, space group Fdd2 with a = 11.691(1), b = 30.200(4), c = 7.1901(9) , V = 2538.7(5) 3, Z = 8, C8H12CuN4O9, Mr = 371.76, Dc = 1.945 g/cm3, m(MoKa) = 1.781 mm-1, F(000) = 1512, the final R = 0.0347 and wR = 0.0766 for 827 observed reflections (I > 2s(I)). The copper atom is square- pyramidally bonded to the exocyclic oxygen atoms of the barbital anions (CuO, 1.976(3)) and the water molecules (CuO, 1.926(4) and 2.164(7) ?. The molecules are held together to form an extensive three-dimensional network via OH贩稯 and NH贩稯 hydrogen-bonded contacts.

Synthesis and Crystal Structure of a Novel Dinuclear Copper(Ⅱ) Complex Containing Benzimidazole Schiff Base Ligand

A novel dinuclear copper（Ⅱ） complex [CuL（NO3）]2·2MeOH was obtained by the coordination reaction of Cu（NO3）2·3H2O with ligand HL （HL=N-（methyl-2-benzimidazol- methylidene）-2-hydroxyaniline）. The single-crystal X-ray analysis has revealed that the complex crystallizes in triclinic, space group P with a=9.535（3）, b=10.009（3）, c=10.666（4） , α=104.303（4）, β=100.105（4）, γ=115.917（4）o, V=839.0（5） 3, C16H16CuN4O5, Mr=407.87, Z=2, Dc=1.614 g/cm3, F（000）=418, μ=1.338 mm-1, R=0.0543 and wR=0.0980. The basic dinuclear copper（Ⅱ） complex units [CuL（NO3）]2 are formed by NO3- as co-bridging ligands and L as NNO tridentate chelate coordinating to the copper ions. The ladder-like one-dimensional chain motifs are formed by O…H-O and O…H-N hydrogen bonds from methanol molecules connecting the dinuclear copper（Ⅱ） units.

Synthesis and Crystal Structure of the Copper(Ⅱ) Complex with 1,10-Phenanthroline-5,6-dione

The complex Cu(phon)(NO3)2(CH3CN) (phon = 1,10-phenanthroline-5,6-dione) has been synthesized and characterized by elemental analysis, infrared and UV-Vis spectra. X-ray diffraction analysis at room temperature indicates that the complex crystallizes in orthorhombic system, space group P212121 with a = 8.353(1), b = 11.299(2), c = 17.764(2) A, V= 1676.5(4) A3, Z = 4, C14H9CuN5O8, Mr = 438.8, Dc = 1.739 g/cm3, F(000) = 884 and μ(MoKα) = 1.361 mm-1. The final R and wR factors for the observed reflections with I > 2σ(I) are 0.0353 and 0.0855, respectively. R = 0.0432 and wR = 0.0899 for all data. The structure of the title complex consists of a neutral mononuclear entity. The central Cu (II) atom is five-coordinated by two nitrogen donors of one ligand, two unidentate NO3- ions and one CH3CN molecule. The coordination geometry of Cu (II) can be considered as a distorted trigonal bipyramidal configuration. The complex ability of the NO3-ion has more effect than that of the ClO4- ion on the structure of the complex.

Synthesis and Crystal Structure of a New Mononuclear Copper( Ⅱ ) Complex: [Cu(BMI)_4(SO_4)]·DMF·2H_2O

A new copper（Ⅱ） complex, [Cu（BMI）4（SO4）]·DMF·2H2O （BMI = benzimidazole）, has been synthesized by the treatment of CuCN with 2-mercaptobenzimidazole in the presence of 1,10-phenanthroline, and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/n with a = 17.6260（4）, b = 11.1252（3）, c = 18.6573（4）A°, β= 107.9010（10）°, V = 3481.45（14）A°^3, Z = 4, C31H35CuN9O7S, Mr= 741.28, F（000） = 1540, Dc = 1.414 g/cm^3,μ = 0.746 mm^-1, the final R = 0.0649 and wR = 0.1609 for 4382 observed reflections with I 〉 2σ（I）. The Cu（Ⅱ） atom is coordinated by five unidentate ligands （one sulfate and four benzimidazole ligands） generated in situ, displaying a slightly distorted square pyramid geometry.

Syntheses and Crystal Structures of Copper(Ⅱ) and Nickel Complexes with 1,2,3-Triazole-carboxylic Acid

Three novel complexes [Cu（L1）2（H2O）2] （1）, [Ni（L1）2（H2O）2]·（H2O）4（2,HL1=5-methyl-1-（4-methylphenyl）-1,2,3-triazole-4-carboxylic acid） and [Ni2 （HL2）2（CH3OH）6]·（CH3OH）2（3,H3L2=1,2,3-triazole-4,5-dicarboxylic acid） were synthesized and characterized by elemental analysis, IR and X-ray diffraction. Complexes 1 and 2 are mononuclear structures, and are assembled into a two-dimensional sheet by C（7） H（7）···O（3） weak interactions or hydrogen-bonding interaction. Complex 3 is a centrosymmetric dinuclear structure, and is assembled into a three-dimensional supramolecular structure by hydrogen-bonding interaction.

Synthesis and Crystal Structure of a New Mononuclear Copper(Ⅱ) Complex with 4,4′,6,6′-Tetrabromo-2,2′- [ethylenedioxybis(nitrilomethylidyne)]diphenol

A new mononuclear Cu（II） complex, [Cu（L）] （H2L = 4,4′,6,6v-tetrabromo-2,2′- [ethylenedioxybis（nitrilomethylidyne）]diphenol）, has been synthesized and structurally characterized. X-ray crystal structure of the complex reveals that the Cu（Ⅱ） ion is four-coordinated by two oxygen atoms and two nitrogen atoms from L2- unit. Crystallographic data： monoclinic, space group P21/n with a = 14.076（2）, b = 6.9801（14）, c = 19.858 （2） A, β= 107.613（2）°, C16n10Br4CuN2O4, Mr = 677.44, V = 1859.6（5） A3, Dc = 2.420 g/cm3,μ = 9.796 mm^-1, F（000） = 1284, Z = 4, the final R = 0.0516 and wR = 0.0938 for 1879 observed reflections with I 〉 2σ（/）. The dihedral angel between the two coordination planes of Cu（1）-N（2）--O（4） and Cu（1 ）-N（ 1 ）-O（3）） is 30.08（6）°.

Synthesis and Crystal Structure of Dinuclear Copper(Ⅱ)Complex Cu_2(μ-PhCOO)_4(amet)_2·2CH_3COCH_3

Reaction of copper powder, dibenzoyl peroxide and 2-amino-4methyl-5-ethoxycarbonyl thiazole (amet) by refluxing in acetone yielded the dinuclearcopper(Ⅱ) complex Cu2 (μ-PhCOO)4 (amet)2- 2CH3COCH3. Crystal structure determination showed that each copper atom is coordinated by four bridged benzoxy and oneamet molecule with an M-M bond (Cu-Cu (A) = 2.6899 (7 ) ), therefore the coor-dination environment around the copper center is a distorted square pyramid with N(1)at the apical position. Blocks of Cu2 (μ-PhCOO)4 (amet)2·2CH3COCH3 crystallize inthe triclinic space group Ph, with Mr= 1100.14, a= 9. 631 (1), b=10. 446 (2), c=12. 758(2) ; a=91. 31 (1), β=95. 50(1),γ= 94. 87(1)°, V=1272. 4(3), Z=1, Dc= 1. 436 g/cm3, F(000) = 570, μ=0. 986 mm-1 and R=0.033, Rw=0.049.The IR spectra, which are of great interest since the molecule has ketone, ester andcarboxylate group simultaneously, are also discussed.

Synthesis and Crystal Structure of the Azo Copper(Ⅱ)-complex

The single crystals of the azo copper（Ⅱ）-complex have been obtained from the solution of the compound dissolved in the ethanol by slow evaporation at room temperature. The structure was successfully determined by single-crystal X-ray diffraction. The crystal is of triclinic system, space group P1 with a = 7.8843（12）, b = 11.5998（17）, c = 13.955（2） A, α = 112.214（2）, β = 95.105（2）, γ = 97.616（2）o, V = 1157.6（3） A^3, Mr = 586.97, Z = 2, F（000） = 600, Dc = 1.684 g/cm^3, μ（MoKα） = 1.120 mm-1, the final R = 0.0419 and wR = 0.1259 for 3475 observed reflections with I 〉 2σ（I）. The coordination around copper（II） atom is a slightly distorted square-pyramidal geometry involving [Cu（C16H11N4O8S）（OH）H2O]-cation, one Na＋ anion and one C2H5OH solvate molecule. The hydrogen bonds and π···π stacking interactions extend the complex into a three-dimensional framework.

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.

Synthesis and Crystal Structure of a New Praseodymium(Ⅲ)-Copper(Ⅱ)Polymeric Complex:〔Pr_(2)Cu_(3)(L_(1))_(6)〕_(n)(H_(2)L_(1)=NH{CH_(2)COOH}_(2))

A novel polymeric Pr 2Cu 3 complex of iminodiacetic acid (H 2L 1=NH{CH 2COOH} 2) Pr 2Cu 3(L 1) 6 n , 1, has been synthesized and structurally characterized. The title complex Pr 2Cu 3O 24 N 6C 24 H 30 ( M r =1258.97) crystallized in trigonal space group P3 c1 (No. 165) with a = 13.424(4), c=14.752(6); V=2303(1) 3; F(000)=1226; λ (Mo Kα )=35.2 cm -1 ; D c =1.820 g·cm -3 ; Z =2. The final R and R w are 0.072 and 0.081 respectively for 1412 reflections with I】3σ(I) . In crystal 1, the Pr 3+ ion is nine coordinated by 6 O atoms from three bidentate chelating carboxylate groups and 3 O atoms from three anti anti bridging carboxylic groups of six L 1 ligands; the Cu 2+ ion is six coordinated by 4 O and 2 N atoms from two pentadentate L 1 ligands. Each pair of Pr(Ⅲ) atoms is bridged by three L 1 ligands, each of which also chelates with one copper(Ⅱ) ion, thus forming a Pr 2Cu 3 cluster unit. Such cluster units are cross linked by flexible L 1 ligands into a three dimensional coordination framework.

Structure Studies on New Types of Macrocyclic Compounds Part Ⅵ. Crystal Structure of Copper(Ⅱ) Complex of 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane-N', N'-diaceticacid

The crystal structure of copper(Ⅱ) complex with a new 14-membered tetraazamacrocyclic ligand 5,5,7,12,12,14-hexamethy1-1,4,8,11-tetraazacyclotetradecane-N'N'-diacetic acid,[CuC16N4H34(CH2COO)(CH2COOH)]·ClO4·0. 5HCIO4·1. 5H2O was determined. Crystallographic data: Mr = 639.22,orthorhombic, space group Pcnb with a=11.743(4),b=16.446(2),c=29.611 (4) A,Z=8,V=5726(3) A3, Dc=1.482 g·cm-3, F(000)=1344,μ=9. 64 cm-1,R=0.063,and Rw=0.067 for 2386 reflections with I≥3σ(I). The structure shows an unusual configuration in which two carboxyl groups were bonded to two neighboring nitrogen atoms of the macrocycle, N1 and N4, and six methyl substituents occur on one side of the macrocycle, while two carboxyl groups on the other side, and central copper(Ⅱ) ion forms a five-coordinated geometry.

Synthesis and Crystal Structure of a New Copper(II) Complex with 4-Cyanobenzoic Acid

A new Cu（Ⅱ） complex [Cu（4-cba）（1,10-phen）（H2O）2]（NO3） （4-Hcba = 4-cyanobenzoic acid） has been synthesized by solvothermal reaction in an ethanol/water mixed solution at 100 ℃ and structurally characterized by single-crystal X-ray diffraction. Crystallographic data： C20H16CuN4O7, Mr= 487.91, triclinic, space group PI, a = 7.8420（2）, b = 9.1070（2）, c = 15.1140（6） A, a = 76.889（9）, β = 81.332（11）, γ = 74.844（ 11）°, V = 1009.89（5） A^3, Z = 2, Dc = 1.605 g/cm^3, F（000） = 498, μ = 1.134 mm^-1, the final R = 0.0379 and wR = 0.0865 for 2977 observed reflections with 1 〉 2σ（Ⅰ）. The Cu（Ⅱ） atom is coordinated by two terminal water molecules, one chelating 1,10-phen molecule and one monodentate 4-cba ligand to form a slightly distorted square pyramid. The title complex molecules are connected through hydrogen bonds and π-π stacking interactions to generate a 2D layered network. The thermogravimetric analysis of the title complex has also been discussed.

Synthesis and Crystal Structure of a Dinuclear Cu(Ⅱ) Complex Based on a Carboxyl-substituted 1H-1,2,3-Triazole and Its DNA Cleavage Activity

The novel dinuclear copper complex [Cu2（H20）2（DMF）2（L）2] （1, H2L = 5-phenyl- 2H-1,2,3-triazole-4-carboxylic acid, DMF = N,N-dimethyl-formamide） has been synthesized and characterized by X-ray single-crystal diffraction. The compound crystallizes in triclinic system, space group P1 with a = 9.591, b = 10.508, c = 15.515A,β = 75.11°, V= 1446.2 A3, Z= 2, Mr = 683.62, Dc = 1.570 g/cm3, μ = 1.531 mm^-1, F（000） = 700, the final R = 0.0404 and wR = 0.1130 for 5327 observed reflections with I 〉 2σ（I）. In each unit of the complex, two Cu2＋ ions coordinated with two triazole ligands to form a dimeric [5,6,5] tricyclic structure. The central Cu atom is five-coordinated, and each copper atom shows a square pyramidal geometry. The crystal structure is stabilized by the inversion-related O-H…O hydrogen bond and C-H…O hydrogen bonding interactions to form a layer structure. Fluorescent spectra show an obvious quenching of fluorescence compared with free 1,2,3-triazole ligand. The results of agarose gel electrophoresis indicate that this complex can cleave the plasmid supercoiled DNA within shorter time in the 50-folds excess of ascorbate under physiological conditions, providing a new example in the research for artificial metal nucleic acid enzyme.

Synthesis, Crystal Structure and Antitumor Activity in Vitro of a New Benzoate Binuclear Cupper(Ⅱ ) Complex

The title compound, [Cu2（C7H5O2）4（C2H6O）2], was synthesized by the reaction of benzoic acid, copper acetate and ethanol in an aqueous solution. Trypan blue dye exclusion method was used in experiment. X-ray single-crystal analysis has revealed that compound 1 （C32H32Cu2O10） crystallizes in the monoclinic system, space group C2/c, Mr = 703.66, a = 47.340（5）, b = 6.6613（4）, c = 22.028（2）A,β = 113.284（4）°, V = 6380.6（10） A^3, Z = 8, Dc= 1.465 g/cm^3, F（000） = 2896,μ = 1.388 mm^-11, the final R = 0.0515 and wR = 0.1172 for 5712 observed reflections with I 〉 2σ（I）. X-ray crystal structure analysis suggests that compound [CH2（C7H5O2）4（C2H6O）2] has a binuclear structure with two Cu（II） atoms coordinated by four benzoate groups and two ethanol molecules. The crystal packing is stabilized by intermolecular O-H...O hydrogen bonds. The compound inhibits the proliferation of K562 cells （chronic myeloid leukemic cells） significantly and dose-dependently in 48 h, and IC50 of K562 is 17.3μg/mL by trypan blue dye exclusion method.