научный журнал по химии Координационная химия ISSN: 0132-344X

CHENG J.T., LIU B., LIU G. — 2013 г.

A new one-dimensional dicyanamide bridged zinc(II) complex containing nitronyl nitroxide radicals [Zn(Hfac)2(NIT-1’-MeBzIm)] (NIT-1-MeBzIm = 2-{2-[(l-methyl)benzimidazolyl]}-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide, Hfac = hexafluoroacetylacetonate) has been prepared and structurally characterized by single-crystal X-ray diffraction. The complex crystallizes in monoclinic, space group P21/c, Z = 4. Crystal data: C25H21F12N4O6Zn, Mr = 766.83, a = 12.1812(13), b = 16.8770(18), c = 15.5230(16) A, = 98.009(2)°, V = 3160.1(6) A3, c = 1.612 g/cm3, (MoK ) = 0.893 mm-1, F(000) = 1540, R = 0.0925 and wR = 0.2652 for 5875 observed reflections with I > 2 (I). The X-ray analysis reveals that the zinc(II) ion is six-coordinated with a distorted octahedral geometry. These units develop as 1D species by intermolecular hydrogen bonds. Magnetic investigation indicates the existence of weak intermolecular interactions is antiferromagnetic with J = 1.35 cm-1, where the spin Hamitonian is defined as H = i,jJi,jSiS within the complex.

CHEN L.J., LI Y.Y., LUO J., SHI D.Y., WANG Y.H., ZHAO J.W. — 2013 г.

A 2D Strandberg-type phosphomolybdate hybrid [Cu(En)(EnH)]2[P2Mo5O23] · 3H2O (I) (En = ethylenediamine) has been successfully synthesized under hydrothermal conditions and structurally characterized by elemental analyses, IR spectrum, UV spectrum and single-crystal X-ray diffraction. The molecular structural unit of I consists of one Strandberg-type [P2Mo5O23]6 subunit, two [Cu(En)(EnH)]3+ cations and three lattice water molecules. The most remarkable feature of I is that each molecular structural unit is connected with adjacent four same units by four [Cu(En)(EnH)]3+ bridges constructing the 2D organic-inorganic hybrid sheet structure with a 4-connected topology. As far as we know, such 2D hybrid sheet structure constructed from Strandberg-type phosphomolybdate units and copper-organic cation bridges is very rare.

AN Y., DONG L.H., LI X.F., YIN Y.S. — 2013 г.

] crystallizes in the triclinic, space group P. The ring-like structure is consisted of two ligands with two copper ions coordinated to the pyridyl nitrogen atoms from two ligands respectively. The largest diameters of the planar-shaped dinuclear ring are about 12.7 A. The adjacent ring-like units are linked via C–H···O hydrogen bonds to generate an infinite linear chain, which are further linked by C–H···Cl hydrogen bonds and weak intermolecular interactions to form a three-dimensional network. . The ring-like structure is consisted of two ligands with two copper ions coordinated to the pyridyl nitrogen atoms from two ligands respectively. The largest diameters of the planar-shaped dinuclear ring are about 12.7 A. The adjacent ring-like units are linked via C–H···O hydrogen bonds to generate an infinite linear chain, which are further linked by C–H···Cl hydrogen bonds and weak intermolecular interactions to form a three-dimensional network.

FENG X., LEI P.P., SHANG J.J., WANG L.Y., ZHAO Y. — 2013 г.

A new lanthanide-organic coordination polymer incorporating both substituted imdazole dicarboxylate and formate auxiliary ligand, namely {[ · 4H2O] · 2H2O}n (I) (H3Eimda = 1H-2-ethyl-4,5-imidazole-dicarboxylic acid), has been prepared and was structurally characterized by elemental analysis, IR and X-ray diffraction. It crystallizes in the monoclinic system, space group of C2/c. The polymer I is built from two dimensional (2D) double decker networks based on the Ln4HEimda4 tetranuclear basic carboxylate as secondary building unit. The extensive hydrogen bonds extend the 2D lamellar network into a 3D supramolecular aggregate. The emission spectrum of polymer I exhibits ligand-to-metal charge-transfer transition luminescence. Variable-temperature magnetic susceptibility measurement reveals that the end to end bridging fashion of formate group results in the depopulation of the stark levels for a single Yb3+ ion and/or possible antiferromagntic interactions between Yb3+ ions within the carboxylato bridged dinuclear unit.

NIU X.C., ZHOU J.M. — 2013 г.

A new 1D Hg(II) coordination polymer, [Hg4(Chbz)4(4,4’-Bipy)2(NO3)4 · H2O]n (I) (Chbz = 2-chlorophenyl, 4,4-Bipy = 4,4-bipyridine), has been synthesized by the in situ synthesis of 2-chlorophenyl from the reaction of 2-chlorobenzoic acid, 4,4-Bipy and mercury salt under hydrothermal conditions and characterized by elemental analysis, IR, TGA and single-crystal X-ray diffraction. Complex I exhibits an interesting 1D infinite zigzag polymeric chain along the x axis. The photoluminescent measurements reveal that complex I exhibits fluorescent emission in the solid state at room temperature.

GAO D.Z., SUN Y.Q., WANG J., XU Y.Y., ZHANG G.Y. — 2013 г.

One novel heterometallic trinuclear complex of macrocyclic oxamide [Ni(CuL)2(HBTC)H2O] (I) (H2L = 2,3-dioxo-5,6,14,15-dibenzo-1,4,8,12-tetraazacyclopentadeca-7,13-dien; H3BTC = 1,3,5-benzenetricarboxylic acid) has been solvothermally synthesized and structurally characterized by elemental analysis, IR spectroscopy, XRD, and single-crystal X-ray diffraction. The crystals crystallize in the monoclinic system, space group P21/c, a = 11.435(3), b = 20.646(5), c = 18.430(5) A, = 94.131(4)°. The structure of I has oxamido-bridged trinuclear [Cu NiII] units and consists of two-dimensional supramolecular architecture formed by strong intermolecular hydrogen bonds. Furthermore, the magnetic properties of complex I was investigated and discussed in detail.

DU J.L., LI L.J., TIAN CH., WANG G.Y., WANG L.Z., YANG X.Y. — 2013 г.

Two novel metal-organic frameworks, [Cd(Bna)(DMF)2(H2O)2]n · nDMF (I) (Bna = 2,2-dihydroxy-l,l-dinaphthyl-3,3-dicarboxylate) and [Cd(Bna)(Bipy)(DMF)2]n (II) (Bipy = 4,4-bipyridine) have been synthesized under mild conditions and structurally characterized. Crystal structural analyses reveal that complex I adots a 1D spiral structure with DMF guest molecules in the spiral by hydrogen bondings. Complex II is constructed by–Cd–Bna–Cd– zigzag chains, which are further connected by Bipy into a 2D sheet. X-ray powder diffraction and thermogravimetric analyses for I and II show that they are highly themally stable in the solid state.

GUO H., LI X.L., LIU G.Z., XIN L.Y. — 2013 г.

A series of Co(II) H2Сpp coordination polymers incorporating different auxiliary ligands, [Co(Сpp)(Phen)(H2O)] (I), {[Co(Bipy)(H2O)4](Cpp)}n (II), and [Co(Cpp)(Bds)(H2O)]n (III) (H2Cpp = 3-(4-carboxyphenyl)propionic acid, Phen = 1,10-phenanthroline, Bipy = 4,4-bipyridyl, and Bds = 4,4-bipyridyl sulfide), were synthesized by the hydrothermal reaction and characterized by single crystal X-ray diffraction, elemental analysis, IR, and TG. Three complexes display from 0D to 1D different structural features under the regulation of distinguishing dipyridyl-type coligands. Complex I possesses a binuclear Co(II) motif constructed by H2Cpp and Phen, which further developing a zipper-like 2D layer via H-bonded and stacking interactions. Complex II displays straight Bipy-bridging 1D chain, and further forming a 3D supramolecular structure by hydrogen-bonded interactions. Complex III exhibits 1D double-chain collectively jointed by Cpp and Bds, which further interlinked into a 3D supramolecular architecture by H-bonded interactions.

CUI L., ZHAO P. CH. — 2013 г.

, Z = 2. space group. The unit cell parameters for I: a = 5.248(1), b = 12.537(2), c = 14.597(2) A, = 91.91(1)°, = 91.22(2)°, = 95.75(1)°, V = 954.8(3) A3, Z = 2.

DU Y.J., LIN C.W., WEI S.Q., XIONG Z.Y., YIN X.H. — 2013 г.

Three novel metal-organic complexes [Co(BDC)(TBZ)2] (I), [Cd2(BDC)2(TBZ)2(H2O)2] · 2(H2O) (II), [Mn2(BDC)(TBZ)4(SO4)] (III) (BDC = 1,4-benzenedicarboxylate, TBZ = thiabendazole) have been prepared and characterized by IR spectrum, elemental analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. X-ray structure analysis reveals that both three complexes are one-dimensional chain polymers. The 1D chain architecture of I is constructed from terephthalic acid and cobalt atoms. A simultaneous presence of chelating and monodentate coordination modes of BDC ligands is observed in complex II. In complex III, the coordinated BDC ligands adopt monodentate mode and with SO anions alternately bridge the Mn2+ ions into 1D chains. The 3D structures of the three complexes are stabilized by stacking interactions and hydrogen-bonds.

YIN X.H., ZHANG Z. — 2013 г.

Two new metal–organic coordination polymers framework formulated as [Cu2(PDA)1.5(2,2’-Bipy)2](H2O)5(NO3) (I) and {[Ni2(Imazameth)2(4,4’-Bipy)] · (ClO4) · CH2OH · H2O}n (II), where H2PDA = 1,4-phenylenediacetic acid, 2,2-Bipy = 2,2-bipyridine, Imazameth = (+/–)2-(4,5-dihydro-4-methyl-4-(1-methylethyl)-5-oxo-1H-imidazol-2-yl)-5-methyl-3-pyridinecarboxylic acid, 4,4-Bipy = 4,4-bipyridine, have been prepared and characterized by spectral method (IR), elemental analysis and single crystal X-ray diffraction techniques. Complex I consists of one-dimensional ladder-like chains featuring binuclear unit in which the two Cu2+ ions have different coordination geometry: one is five-coordinated, the other is six-coordinated. Complex II is a new two-dimensional copper complex with the peculiarity of having the 4,4-Bipy ligand and Imazameth ligand acting as bridge to form planar network polymer. Both I and II exist abundant hydrogen bonds. It is result in the formation of a supermolecular crystal, in which they seem to be effective in the stabilization of the structure.

CHENG K., ZHANG X.L. — 2013 г.

Two new coordination polymers, [Pb(IDPT)2(NO3)2] (I) and [Mn(IDPT)(SO4)(H2O)2] (II) (IDPT = imidazo[4,5-f][1,10]phenanthroline), were synthesized by hydrothermal method and characterized by elemental analysis and single-crystal X-ray diffraction technique. The results reveal that the complex I belongs to monoclinic crystal system, space group C2/c and complex II belongs to monoclinic crystal system, P21/c space group. The cell parameters are: a = 19.1970(13), b = 7.3875(5), c = 17.3825(12) A, ? = 100.47(10)°, V = 2424.0(3) A3, Z = 4, F(000) = 1488 for I; a = 10.9135(6), b = 7.0230(4), c = 19.7034(10) A, ? = 99.32(10)°, V = 1490.25(14) A3, Z = 4, F(000) = 828 for II. In the structure of complex I, the metal center Pb(II) is six-coordinated, displays an octahedral geometry. Each molecule is further connected with neighboring one via interactions into 1D chain. In complex II, Mn(II) is six-coordinated to form a distorted octahedral geometry. Compound II displays 1D supramolecular chain formed through hydrogen bonds. Additionally, the fluorescent properties for the complexes were investigated. Complexes I and II exhibit strong photoluminescence with emission maximum at 583 and 529 nm at room temperature.

FAN P., GE C.H., LIU J., WANG F.F., WANG L.J., ZHANG R., ZHANG X.D. — 2013 г.

The synthesis and characterization of Mn(II) and Cu(II) complexes with the general formula [Mn(Phen)2(Pfbz)2](Hpfbz) (I) and [Cu2(Bipy)2(Pfbz)4] (II) (Phen = 1,10-phenanthroline, Bipy = 2,2-bipyridine, Pfbz = pentafluorobenzoate) are reported. I crystallizes in triclinic crystal system, space group P with a = 9.755(1), b = 11.302(1), c = 20.064(2) A, = 95.799(2)°, = 90.176(2)°, = 113.993(2)°, and Z = 2. Complex II crystallizes in triclinic crystal system, space group P with a = 9.661(1), b = 9.951(1), c = 12.891(1) A, = 102.943(2)°, = 98.972(2)°, = 96.746(2)°, and Z = 1. Of particular interest, intricate C–H···F and F···F interactions in the two crystals play important role in the formation of three dimensional supramolecular networks. F(lp)... (lp = lone pair) interaction is recognized in the solid-state structure of II.

BUDANTSEVA N.A., FEDOSSEEV A.M., GOGOLEV A.V., GRIGORIEV M.S. — 2013 г.

The M–O bond lengths in the lanthanide series show a well-known behaviour due to lanthanide contraction, including so-called “gadolinium break”. All three bond lengths show a good linear correlation with Shannon ionic radii for Y3+ and Ln3+ ions with coordination number 9. Nevertheless, the slopes of these dependences are different (0.957(16) for OH-groups, 0.85(2) for carboxylate groups and 1.080(17) for water molecules) and differ from unity due to a layer nature of the structures. The ionic radii for Pu3+ and Am3+ with coordination number 9 are absent in the Shannon system of ionic radii. From our data, we can propose the values 1.172 and 1.156 A for Pu3+, and Am3+, respectively. In all crystals the structure is stabilized through extensive hydrogen bonding involving carboxylic and hydroxyl groups and water molecules.

LIU S.L., PENG H.M., YU L.C. — 2013 г.

A Co(II) complex [Co3(L)4(H2O)6] · 2Cl (I), where L is salicylaldehyde-aminoacetic acid Schiff base, was synthesized and characterized via elemental analysis, UV, and single crystal X-ray crystallography. Complex I crystallizes in the orthorhombic system, space group Pbcn with lattice parameters a = 9.569(4), b = 12.301(5), c = 36.931(14) A, V = 4347(3) A3, Z = 4, = 1.608 mg m-3. At the same time, the binding reaction between complex I and bovine serum albumin (BSA) was studied by fluorescence spectroscopy combined with UV-Vis absorption measurements under simulative physiological conditions. The results indicated that its combination reaction is mainly a static quenching process. Complex I bound BSA with a molar ratio of 1 : 1 and the binding constant KA values are 3.86 ? 105 L mol-1 (25°C) and 1.17 ? 105 L mol-1 (36°C). The shortest binding distance r between the donor BSA and acceptor (complex I) is 2.49 nm, which affirms that complex I has partly inserted into the hydrophobic pocket of BSA.

LIU R.N., XIONG C.X., ZHAO S.P. — 2013 г.

Three new complexes [Fe(L1)2(NCS)2(CH3OH)2] (I), [Co(L2)2(CH3OH)2(H2O)2](ClO4)2 · L2 · 2H2O (II), and [Co(L1)3(H2O)2](ClO4)2 · L1 (III) (L1 = 1,4-bis(3-pyridyl)-2,3-diaza-1,3-butadiene; L2 = 1,4-bis(4-pyridyl)-2,3-diaza-1,3-butadiene) have been prepared and structurally characterized by X-ray single crystall diffraction. Complexes I and II are mononuclear. Complex III has a 1D chain structure. Complex I is assembled by intermolecular O–H...N hydrogen bonds leading to 2D structure. In complex II, mononuclear complex cations are linked into 1D chain through hydrogen bonds. Then the chains get into 2D structure by intermolecular O–H···N hydrogen bonds too. In complex III, coordinated ligand L1 acts as a ditopic bridge to produce 1D coordination chain. The self-complementary intermolecular O–H···N hydrogen bonds assemble the chains into 2D sheets.

CHENG X.S., QIAN S.S., YOU Z.L., ZHU H.L. — 2013 г.

A new centrosymmetric mononuclear nickel(II) complex, [Ni(IIP)2] (I), and a new end-on azido-bridged dinuclear copper(II) complex, [ ] · MeOH (II) (IIP = 2-iminomethyl-4,6-diiodophenolate, PMP = 2-[(2-phenylaminoethylimino)methyl]phenolate), have been prepared from similar tridentate Schiff bases derived from N-phenylethane-1,2-diamine with 3,5-diiodosalicylaldehyde and salicylaldehyde, respectively. The complexes were characterized by elemental analysis, infrared spectra, and single-crystal X-ray diffraction. Complex I crystallizes in the monoclinic space group P21/c with unit cell dimensions a = 4.936(1), b = 11.779(3), c = 15.789(4) A, = 90.722(3)°, V = 918.0(4) A3, Z = 2, R1 = 0.0267, and wR2 = 0.0546. Complex II crystallizes in the orthorhombic space group Pna21 with unit cell dimensions a = 23.370(2), b = 12.210(1), c = 11.438(1) A, V = 3263.8(5) A3, Z = 4, R1 = 0.0461, and wR2 = 0.0891. The Ni atom in I is in a square planar coordination, and the Cu atoms in II are in square pyramidal coordination.

CHENG X.S., QIAN S.S., REN J.Q., YOU Z.L., ZHU H.L. — 2013 г.

Two new structurally similar mononuclear Schiff base zinc(II) complexes, [ZnBr(ClMP)] (I) and [ZnCl(NMP)] (II) (ClMP = 4-chloro-2-[(3-morpholin-4-ylpropylimino)methyl]phenolate; NMP = 4-nitro-2-[(3-morpholin-4-ylpropylimino)methyl]phenolate), and two new dinuclear Schiff base zinc(II) complexes, [Zn2(EMP)2I2] (III), and [Zn2(MPA)(CH3OH)2(N3)2] (IV) (EMP = 5-diethylamino-2-[(2-dimethylaminoethylimino)methyl]phenolate; MPA = N,N-bis(3-methoxysalicylidene)propane-1,3-diamine), have been prepared and characterized mainly by single-cyrstal X-ray diffraction. Complex I crystallizes in the monoclinic space group P21/n with unit cell dimensions: a = 15.116(3), b = 9.465(1), c = 23.714(4) A, = 104.358(2)°, V = 3286.9(8) A3, Z = 8, R1 = 0.0439, and wR2 = 0.0736. Complex II crystallizes in the monoclinic space group P21/c with unit cell dimensions: a = 7.253(2), b = 16.652(4), c = 13.568(3) A, = 96.600(2)°, V = 1627.8(6) A3, Z = 4, R1 = 0.0417, and wR2 = 0.0809. Complex III crystallizes in the monoclinic space group C2/c with unit cell dimensions: a = 27.962(2), b = 8.246(2), c = 31.605(3) A, = 90.343(2)°, V = 7287.4(15) A3, Z = 8, R1 = 0.0721, and wR2 = 0.1709. Complex IV crystallizes in the monoclinic space group C2/c with unit cell dimensions: a = 20.483(3), b = 11.344(2), c = 14.909(3) A, = 131.650(1)°, V = 2588.6(7) A3, Z = 4, R1 = 0.0343, and wR2 = 0.0792. Each Zn atom in I and II are four-coordinated in a tetrahedral geometry by the NNO donor set of the Schiff base ligand and one halide atom. The Zn atoms in III are in square pyramidal coordination, and those in IV are in octahedral and tetrahedral coordination. Thermal stability and fluorescence properties of the complexes I and II have also been determined.

LIU R.N., XIONG C.X., ZHAO S.P. — 2013 г.

Two new lanthanide-radical complexes [Ln(Hfac)3(NIT-4PhAllO)2](Ln(III) = Gd (I), Tb (II); Hfac = hexafluoroacetylacetonate; NIT-4PhAllO = 4-allyloxyphenyl-4,4,5,5-tetramethylimidazoline-1-oxyl-3-oxide) have been prepared and characterized in structurally as well as magnetically. Single crystal X-ray diffraction analyses reveal that two complexes are isostructural with mononuclear tri-spin structure, in which the metal ions are eight-coordinated in distorted dodecahedron geometry. The nitronyl nitroxide radicals act as monodentate ligands towards Ln(Hfac)3 unit through the oxygen atom of the nitronyl nitroxide group. Magnetic studies reveal that the Gd-coordinated nitroxide interaction is ferromagnetic.

HU R.G., LUO X.Q., RAN L., ZENG J., ZHANG G.L. — 2013 г.

A new bimetallic cluster complex with the formular {[Cu(Phen)2]2V4O12} · MeOH · 5H2O has been synthesized and structurally characterized by elemental analyses, IR spectrum, and single crystal X-ray diffraction. The heterobimetallic cluster complex is composed of a discrete V4O cluster covalently attached to two [Cu(Phen)2] fragments. The nonclassical hydrogen bonds and stacking contribute to the formation of the three-dimensional supramolecular structure. Microdilution broth method indicated that the complex showed significant activity against B. subtilis, S. aureus, and E. coli.