Synthesis, Crystal Structure and Pyrolysis of a Heterobimetallic Peroxo-titanium（IV） Nitrilotriacetate Complex

A new heterobimetallic nitrilotriacetatoperoxotitanate complex with the formula of [Mn(H2O)5]2[Ti(O2)2O(nta)2]·7H2O (1, C6H6O6N = H3nta) has been isolated in pure crystals. It was characterized by elemental analyses, IR, thermal analysis (TGA) and single-crystal X-ray diffraction. Complex 1 crystallizes in monoclinic, space group C2/c with a = 15.088(3), b = 13.311(3), c = 17.741(4) , β = 100.92(3)°, Z = 4, V = 3498.6(12) 3, Mr = 968.19, Dc = 1.838 g/cm3, μ = 1.266 mm-1, F(000) = 1992, R = 0.0337 and wR = 0.0819. Single-crystal X-ray analysis reveals that the titanium atom is N,O,O',O'-chelated by the nitrilotriacetate and O,O'-chelated by the peroxo group, and is coordinated to the bridging O atom in an overall pentagonal-bipyramidal geometry. The manganese ions in the compound are both 6-coordinated by five water molecules and one bridged carboxylato oxygen atom. A decameric water cluster consisting of a cyclic water hexamer in a boat fashion is also found in complex 1. The TGA and XRD results prove that 1 undergoes facile thermal decomposition to form the mixture of Mn2O3 and TiO2 at 600～800 ℃, and pure MnTiO3 at 900 ℃.     

CRYSTAL STRUCTURE OF (NH_4)_(11)[Na(H_2O)_2P_4W_(14)O_(58)] ·12H_2O

<正> (NH4)11[Na(H2O)2P4W14O58)·12H2O, Mr = 4099. 39, triclinic, space group P1, a = 14. 376(2), b = 19.861(9), c=13. 010(3)(?) , α=104. 68(2), β=91. 37(1), γ= 104. 05(2)°, V = 3471. 1 (?)3, Z = 2, Dc=3. 922g/cm3, μ (MoKα) = 238. 274cm-1, F(000) = 3664, R = 0.0510, Rw = 0. 0665 for 9260 observed reflections with I> 3σ(I). The polyanion [Na(H2O)2P4W14O58]11- consists of two PW7O29 subunits anisostructurally, two linkage phosphorous atoms and one sodium ion with two water ligands as well. The geometries of tungsten atoms within these two subunits are almost the same as those in K12P4W14O58· 21H2O[2]. The four phosphorous atoms are in PO4 coordinations. The sodium ion locates nearly at the center of the polyanion, and is coordinated by two water molecules, five oxygen atoms of the anion and one phosphorous atom with Na-P = 3. 053(3) (?). Due to the presence of the sodium atom, the interactions between oxygen and tungsten atoms in the polyanion are somewhat weakened.     

Synthesis, Crystal Structure and Properties of Complex VO（C10H9NO3） （C13H10NO2）

Complex VO(C10H9NO3)(C13H10NO2)(C10H9NO2-3=N-salicylidene-L-alaninate, C13H10NO-2=N-phenylbenzohydroxamate) was synthesized and characterized by means of elemental analysis, IR, UV, 1H NMR spectroscopies, cyclic voltammetry and single crystal X-ray diffraction. The complex crystallized in a monoclinic system with space group P21 and crystal cell parameters a=0.9720(1) nm, b=1.8274(2) nm, c=1.2542(1) nm, β=104.868(9)°, V=2.1532(4) nm3, Mr=470.34, Z=2. The two oxygen atoms and the one nitrogen atom of the tridentate Schiff base ligand and the one oxime oxygen atom of the hydroxamate ligand coordinate to the vanadium atom, forming an equatorial plane, the two axial positions are respectively occupied by the oxygen atom of the oxovanadium and the carbonyl oxygen atom of the hydroxamate and the vanadium atom exhibits a distorted octahedral VO(ONO)(OO) coordination sphere. The 1H NMR spectrum suggests that the two isomers, endo and exo in a molar ratio of 1/1.7, coexist in the solution of the title complex in CDCl3. There exists a quasi-reversible one-electron redox reaction corresponding to VⅤ/VⅥ couple in the three non-aqueous solvents, and the redox potential E1/2 of the title complex substantially shifts in the direction of the positive voltage increase in the order: CH2Cl2＜CH3CN＜DMF.     

SYNTHESIS AND STRUCTURE OF THE PEROXOVANADIUM (V) COMPLEX CONTAINING NITRILOTRIACETATE Na_2[VO (O_2) N-(CH_2COO)_3]·5H_2O

<正> Na2[VO(O2)N(CH2COO)3] · 5H2O, Mr= 423. 11, monoclinic, space group P21/c, a = 6. 283(3), b = 20. 378(6), c=12. 056(4)(?) , β=102. 96 (3)°, V = 1507. 9(?)3, Z = 4, Dc= 1. 864 g/cm3. λ(MoKα) = 0. 71069A , F(000) = 864. Final R = 0. 037 and Rw = 0. 046 for 1658 observed reflections with I>10σ (I). The structure of the anion of the title complex shows that the vanadium atom is coordinated by one vanadyl oxygen atom, two oxygen atoms of the peroxp-group, three oxygen atoms and one nitrogen atom from the NTA ligand to form a distorted pentagonal bipyramid.     

Unexpected Synthesis and Crystal Structure of Macrocyclic Nickel Complex Involving Rare S-Cl Bond

A novel complex of [NiL(OOCNH2C2H3SClO3)]·H2O was obtained unexpectedly by the reaction of [Ni(rac-L)](ClO4)2 with l-cysteine (L=5,5,7,12,12,14-hexamethyl-1,4,8,11-tetra- azacyclotetradecane), and characterized by EA, IR, ESI-MS and single-crystal X-ray diffraction. It crystallizes in the orthorhombic system, space group P212121 with a=9.211(12), b=14.942(19), c=19.002(2), Mr=563.80, V=2615.3(6)3 , Z=4, Dc=1.432 g/cm3 , F(000)=1204, μ=0.966 mm-1 , the final R=0.0565 and wR=0.1515. The central nickel(Ⅱ) ion displays a distorted six-coordinate octahedral coordination geometry by coordination with four nitrogen atoms of L, and one oxygen and one nitrogen atoms of l-cysteine. The sulfur atom of l-cysteine instead of oxygen atom links directly with the chlorine atom of perchlorate. The title complex is the first example of perchlorate salt involving the sulfur atom.     

Preparation,Crystal Structure,Thermal Decomposition and Explosive Properties of K2（tza）2（H2O） （tza=Tetrazole-1-acetic Acid）

A new energetic compound based on the tetrazole-1-acetic acid (tza) and potassium(I) salt, K2(tza)2(H2O), was synthesized and characterized by elemental analysis and FT-IR spectrum. Its crystal structure was determined by single-crystal X-ray diffraction analysis. The results show that the crystal belongs to the orthorhombic system, space group Pna21 with a = 1.11972(17) nm, b = 0.46647(7) nm, c = 2.5158(4) nm, V = 1.3140(3) nm3, K2C6H8N8O5, Mr = 350.40 g·mol-1, Dc = 1.771 g·cm-3, μ(MoKα) = 0.759 mm-1, F(000) = 712, Z = 4, R = 0.023 and wR = 0.0527 for 2961 observed reflections (I > 2σ(I)). The K(I) cation is six-coordinated with four O atoms from three carboxylate groups, one O atom from one H2O molecule and one N atom from tetrazolyl ring, in which each tza is coordinated in a tridentate chelating bridging coordination mode. The thermal decomposition mechanism of the title complex was studied by DSC and TG-DTG techniques. Under nitrogen atmosphere at a heating rate of 10 K·min-1, the thermal decomposition of the complex contains one main exothermic process between 191.7 and 243.8 ℃ in the DSC curve. Its combustion heat was mensurated by oxygen bomb calorimetry. The non-isothermal kinetics parameters were calculated by the Kissinger's method and Ozawa-Doyle's method, respectively. The sensitivity properties of K2(tza)2(H2O) were also determined with standard methods, which was very sensitive to flame.     

Synthesis and Characterization of Two Binuclear Macrocyclic Zinc(Ⅱ) Complexes by Anion Exchange

Two macrocyclic zinc(II) complexes {[ZnL(VO3)2]·0.33H2O}n(1) and [ZnL(H2O)2][Ni(CN)4](2)(L = 5,5,7,12,12,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) have been obtained from the reactions of [ZnL](ClO4)2 with NH4VO3 and K2[Ni(CN)4], respectively, and structurally characterized by elemental analysis, IR, XRPD, TG and X-ray diffraction. Single-crystal X-ray diffraction analyses indicated that the Zn(II) atom lies on an inversion center and is octahedrally coordinated by four nitrogen atoms of the tetradentate macrocyclic ligand in the equatorial plane and two oxygen atoms of [VO4] tetrahedra in the axial positions in 1, and two oxygen atoms of two water molecules in 2. Complex 1 shows a three-dimensional structure, which is constructed by the links of [VO3]nn- chains with [ZnL]2+, forming one-dimensional channels occupied by guest water molecules. The monomers of [ZnL(H2O)2]2+ and [Ni(CN)4]2- are connected through the intermolecular hydrogen bonds to form a two-dimensional sheet in complex 2.     

EXAFS and FTIR structural characterization for the crystal of monomeric tetraphenylporphyrinato gadolinium:[Gd(TPP)acac 8H_2O.3TCB]

The coordination number of the gadolinium atom and bond distances in the crystal of inonomeric porphyrinate,[Gd(TPP)acac-8H2O 3TCB] (TCB: 1,2,4-trichlorobenzene,acac: anion of acetylacetone),were determined by EXAFS method.The Gd atom is eight-coordinated to the four nitrogen atoms of a tetraphenylporphyrin ring,to the two oxygen atoms of one acetylacetonato anion and to two water molecules with Gd-N=0.232 nm,Gd-O=0.243 nm.     

Synthesis and Crystal Structure of a New [Mn_2Ni_2] Cubane Complex

A new Mn2Ni2 cubane complex has been synthesized and characterized by single-crystal X-ray diffraction,FT IR spectra and elemental analysis.The title compound [MnIII2NiII2(hmp)4(N3)4(O2CR)2](hmp-is the anion of 2-pyridinemethanol and O2CR-is α-na-phthaleneacetate)crystallizes in the monoclinic system,space group P21/c with a = 10.519(5),b = 22.109(10),c = 23.235(9),β = 106.096(17)o,C48H42Mn2N16Ni2O8,Mr = 1198.28,V = 5192(4)3,Dc = 1.533 g/cm3,F(000)= 2448,μ = 1.258 cm1,Z = 4,the final R = 0.0875 and wR = 0.2020 for 3398 reflections with I > 2σ(I).X-ray diffraction analysis reveals that each Mn(III)center is octahedrally coordinated by two nitrogen atoms of azide anions and three oxygen atoms from three 2-pyridinemethanol anion ligands together with one oxygen atom from naphthaleneacetate.Each Ni(II)is octahedrally coordinated by two nitrogen atoms of 2-pyridinemethanol anion ligands as well as three oxygen atoms from three 2-pyridinemethanol anion ligands and one oxygen atom from naphthaleneacetate.     

CRYSTAL STRUCTURES OF COPPER (Ⅱ) AND COBALT (Ⅲ) COM- PLEXES OF o-HYDROXYBENZYLGLYCINATE (HBG)

<正> The structures of two complexes C(CuOC6H4CH2NHCH2COO)2 (H2 O)]·H2P(1) and [Co(NH3)6[Co(OC6H4CH2NHCH2COO)2]2[C1]·10H2O (2) were determined by X-ray analyses. Compound (1) crystallizes in the orthorhombic space group P212121 with a=11. 357(1),b= 24. 304(2),c=7.317(4) A,Z= 4;While compound (2) in the monoclinic space group A2/a(C2/c) with a=23. 486(9) ,b=26. 605(6) ,c= 10. 542(1) A,γ= 128. 42(4)°,Z= 4. In compound (1),two Cu(Ⅱ) ions are bonded together by the phenolic oxygen atoms of two tridentate chelating ligands and each of them is separately coordinated by the carboxyl oxygen,amino nitrogen of each chelate ligand and by the fifth oxygen atom as well (from aqua or the carbonyl group in adjacent molecule). Thus the coordination of each Cu(Ⅱ) is a square pyramid with distances of 1. 93- 1. 97A to the four corner atoms and 2. 30 and 2. 32 A to the apex atoms. The whole molecule has an approximately planar configuratioir with the two pyramid apexes pointing towards one side. Compound (2) consists of     

Syntheses, Structures and Characterizations of Two New Vanadium(V) Complexes: [PyH][V~vO_2(C_(14)H_9N_2O_3Br)] and [V~vO(C_(14)H_9N_2O_3Br)(OCH_3)]

<正>The new oxovanadium (V) complex, [PyH][VO2(L)] 1 (salicyladehyde 5-bromo salicyloylhydrazone is abbreviated as H2L; Hpy is protonated pyridine) was obtained from a refluxed solution of VOSO4 and H2L in acetonitrile-methanol-pyridine. Similarly, another new complex, [VO(L)(OCH3)] 2 was synthesized by refluxing VOSO4 and H2L in methanol-pyridine. Crystal data for 1: C19H15N3O5BrV, Mr= 496.2, monoclinic, P21/n, a = 7.1885(3), b = 9.2718(3), c = 28.803(1) A, β = 96.185(1)°, Z = 4 and V = 1908.6(1) A3; for 2: C15H12N2O5BrV, Mr= 431.1, monoclinic, P2,/n, a = 12.202(2), b = 8.045(2), c = 16.604(3) A, β = 101.29(3)°, Z = 4 and V = 1598.4(2) A3. The structures of 1 and 2 have been determined by X-ray analyses and reveal that the coordination environments of V atoms in both complexes are of square-based pyramid. Three of the four based donor atoms are from the tridentate "ONO" donor ligand while the fourth is one terminal oxygen atom with the V(1) - O(3) distance 1.646(4) A for 1 and one -OCH3 group with the V     

CRYSTAL STRUCTURE OF DISODIUM DIAZA-18-CROWN-6-N, N''''-DIACETATE PENTAHYDRATE

<正> The title compound was prepared from the reaction of diaza-18-crown-6 and sodium chloroacetate in aqueous solution and crystallized from ethanol solution by standing for a long time. The complex [Na(C16H28N2O8)·Na(H2O)5]2Cl-·2H2O+·H2O (Mr = 655. 45) crystalizes in triclinic system,space group P1 with a = 9. 623(2),b = 10. 902(3),c=15. 867(3) A ;α= 104. 63(2),β= 105. 42(2),γ=99. 88(2)°,V = 1502. 3A3,Dc=1. 09gcm-3,Z = 2,F(000) = 516,final R=0. 075 for 3218 observed reflections. The donor atoms O(4) ,O(7) ,O(13) ,O(16) ,N(1) and N(10) from the crown ether as well as the oxygen atoms O(21) and O(26) from two car boxy lato anions are coordinated cooperatively to the Na(1)+ ion to form crown ether solvated cation in a tetragonal prismatic geometry. The O(22) of one carboxylato anion, which does not coordinate the Na(1) + ion,interacts with the Na(2)+ion together with the oxygen atoms of five water molecules to form a hydrated cation having a deformed octahedral configuration.     

A CLUSTER COMPOUND WITH DI-ENDOXYGEN LIGANDS——THE CRYSTAL AND MOLECULAR STRUCTURE OF [Fe(MOS_4O)_2][N(C_2H_5)_4]3

[Fe(MoS_4O)_2] [N(C_2H_3)_4]_3 cluster compound with di-end-oxygen ligands has been prepared and characterized by the X-ray diffraction method. The compound crystallizes in a monoclinic space group P2_1/n with lattice parameters a=13.019(4), b=16.959(5), c=18.234(5), β=97.34(2)(°), Z=4. The final agreement factors are R=0.0740, Rw=0.0598. The terminal bond length, Mo-S_t and bridged one, MO-S_b for the compound are much longer than the counterpart without end-oxygen ligand. It possibly suggests that low valence of molybdenum and smaller electronegativity of sulphur than oxygen lead to the charge transfer as S→Mo→O.     

Synthesis and Structure Study of Molybdenum Complex Mo[o-NHCOCH_3-m-NO_2C_6H_3COOH]_2_O2Cl_2·PhCl

The crystal and molecular structures of molybdenum complex, Mo [ o- NHCOCH3- m-NO2C6H3COOH]2O2Cl2.PhCl are reported. The crystal belongs to space group Cc of monoclinic system with unit cell parameters:α= 11. 214 (3) A .b= 19. 544 (4 ) A . c = 14. 091 (6) A .β=94.06(3)°,V'=3080.3 A3 and Z=4. The structure was refined to R=0. 061.The coordination number for the Mo atom Is six. The coordination polyhedron formed by four O atoms and two Cl atoms around the Mo atom is a distorted octahedron. Four O atoms and one Mo atom construct a plane. Two benzyl planes in coordinate groups and the benzyl plane of solvent are almost parallel. The quantum-chemical calculations were carried out. There are hydrogen bonds in the Complex. The EHMO calculations and the existence of hydrogen bonds prove that the O atoms are stronger coordinated atoms in the carbonyls than in the carboxyls.     

Synthesis, Crystal Structure, Thermal Behavior and Photoluminescent Property of Complex [Zn(L)(SO4)]·0.5H2O

Complex [Zn(L)(SO4)]·0.5H2O (L= 2-(2-chloro-6-fluorophenyl)-1H-imidazo[4,5-f][1,10]phenanthroline) has been synthesized under hydrothermal conditions. The compound was characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21 /n with a = 9.9916(7), b = 12.3834(9), c = 29.259(2) , β = 97.7720(10)°, V = 3587.0(4)3 , Z = 2, C76H41Cl4F4N16O9S2Zn2 , Mr = 1734.91, Dc = 1.606 g/cm 3 , F(000) = 1754, μ(MoKa) = 0.959 mm -1 , R = 0.0492 and wR = 0.1385. The asymmetric unit of 1 contains one Zn(II) atom, two L ligands, one sulfate anion and half a water molecule. Each Zn(II) atom is five-coordinated by four nitrogen atoms from two different L ligands and one sulfate oxygen atom in a tetragonal pyramidal coordination environment. The N-H···O hydrogen bonds link the discrete structure of 1 into a 2D supramolecular architecture. The photoluminescent property of 1 has also been studied in the solid state at room temperature.     

SYNTHESIS, CHARACTERIZATION AND STRUCTURE OF [Co(DBP)_2·3Py]_2·2CHCl_3

The mixed ligand complex of cobalt with dibutylphosphate (HDBP) and pyridine has been synthesized. Elemental analysis yields the result that the formula of this compound is Co(DBP)_2·3Py·CHCl_3 (Py=pyridine). The thermal analsyis, visible spectra and magnetic properties of it have been studied as well. Single crystal structural analysis shows that the crystal is triclinic with space group P and the unit cell parameters are as follows:a=14.490(10), α=90.37(4)°,b=15.721(7), β=96.04(5)°,c=20.109(12), γ=105.63(4)°.The final R factor is 0.0773. Two Co atoms are connected by two bridging DBP groups to form a dinuclear molecule [Co(DBP)_2·3Py]_2 which has a C_s, symmetry. Each cell contains two dinuclear molecules and four chloroform molecules. The cobalt is coordinated in an octahedral arrangement by three oxygen atoms and three nitrogen atoms, of which one oxygen atom comes from a monodentate DBP group, two oxygen atoms from two bridging DBP groups, and the three nitrogen atoms from the three pyridi     

Synthesis and crystal structure of heteronuclear La(Ⅲ)-Cu(Ⅱ) complex {[LaCu_2(NTA)_2(4,4'-bpy)(H_2O)_3]NO_3·5H_2O}_n

A novel La(Ⅲ)-Cu(Ⅱ)heterometallic coordination polymer {[LaCu2(NTA)2(4,4'-bpy)(H2O)3]NO3 5H2O}n,where H3NTA denotes nitrilotriacetic acid and 4,4'-bpy denotes 4,4'-bipyridine,was synthesized and characterized by IR spectrum,elemental analysis and X-ray diffraction.The complex crystallizes in the triclnic space group PT with cell parameters a=1.33710(10)nm,b=1.44530(10)nm,c=1.0949(2)nm,α=71.905(7),β=74.327(7),γ=64.427(9),V=1.7912(4)nm3 and Z=2.It consists of heterometallic units,in which each La(Ⅲ)ion is coordinated in a distorted mono-capped square antiprism by three oxygen atoms from water molecules and six carboxyl oxygen atoms from five NTA3-ions,and each Cu(Ⅱ)ion is coordinated by one nitrogen atom from 4,4'-bpy and one nitrogen atom,three oxygen atoms from NTA3-.In the title complex,La(Ⅲ)ions and Cu(Ⅱ)ions are connected by the heterometallic bridging of NTA3-,constructing a two-dimensional network structure along the [110].And it is extended into an infinite three-dimensional network struc     

Synthesis and Crystal Structure of [Cu3(dmpzm)4(μ-1,3-dca)2(dca)4]·2H2O (dmpzm = 1,1·-Methylenebis-(3,5-dimethyl-1H-pyrazole), dca = dicyanamide)

The title compound, [Cu3(dmpzm)4(μ-1,3-dca)2(dca)4]·2H2O (dmpzm = 1,1'-methyle- nebis(3,5-dimethyl-1H-pyrazole), dca = dicyanamide) 1·2H2O, was synthesized via the reaction of CuCl2·2H2O with dmpzm and Na(dca), and characterized by elemental analysis and IR spectra. 1·2H2O crystallizes in the monoclinic system, space group C2/m with a = 13.578(3), b = 16.769(3), c = 14.769(3)(A),β=104.10(3)°, V = 3261.4(11)(A)3, Z = 2, Dc = 1.466 g/cm3, T = 153(2) K, C56H68N34O2Cu3, Mr = 1440.09, F(000) = 1490, μ(MoKα) = 1.040 mm(1, S = 1.150, R = 0.0553 and wR = 0.1123 for 2744 observed reflections with I > 2σ(I). The central copper atom is chelated by two dmpzm ligands and coordinated by two bridging dca anions, forming a slightly distorted octahedral geometry. The two external copper atoms adopt a square-pyramidal coordination geometry, coor- dinated by one chelating dmpzm ligand and one bridging and two terminal dca anions. Two inter- molecular hydrogen bonding interactions result in the formation of a 2D (4,4) hydrogen-bonded network.     

丙酮酸异烟酰腙四核有机锡配合物的合成、表征及{[nBu2Sn(C9H8N3O3)O]SnBu3n}2的晶体结构

The tetranuclear alkyltin(Ⅳ) compounds {[R2Sn(C9H8N3O3)O]SnR3}2 [R=n-Bu (1), 4-CNC6H4CH2 (2),C6H5CH2 (3), 4-ClC6H4CH2 (4)] were prepared by the reaction of Schiff base ligand pyruvic acid isonicotinyl hydrazone with (R3Sn)2O in the corresponding molar ratio of 1:1. All compounds have been characterized by elemental analysis, IR and ^1H NMR spectra. The crystal structure of compound 1 was determined by X-ray single crystal diffractional analysis. This compound exhibits a dimeric structure containing distannoxane units with two types of the tin atoms. For the first tin atom, it appears to be seven-coordinated with a distorted pentagonal bipyramid geometry, and the other is five-coordinated with a distorted trigonal bipyramidal geometry. The molecules are packed in the unit cell in two-dimensional network structure through an interaction between the N atoms of the pyridine and the tin atoms of an adjacent molecule.     

Synthesis,Structure Characterization and Biological Activity of a Novel Amino Acid Salt(HAla)_8(H_3O)_(10)[PMo_(12)O_(40)]_6·22H_2O

A novel compound was synthesized and characterized by means of elemental analysis, IR and UV spectra, TG, CV and single crystal X-ray diffraction. The compound crystallized in an orthorhombic space group C222 with a = 1. 622 4(3) nm, b=3. 498 4(7) nm, c=l. 301 5(3) nm,V=7. 387(3) nm3, Z = 6, R1 = 0. 037 3, wR2 = 0. 114 0. The Ala (Ala = alanine) molecules were protonated at the amino nitrogen N (1) and the C (2) of Ala group with the terminal oxygen atom O(15), O(14), O(26) and O(27) of the polyoxometalates participating in the hydrogen bond network. The anti-tumor activity of the title compound was estimated against Hela and Pc-3m cancer cells.