Syntheses, Crystal Structures and Characterization of Layered and Layer-pillared Zinc Arsonates

Two zinc arsonate coordination polymers, Zn(4-apa)·H2O (1, 4-apaH2 = 4-amino- phenylarsonatic acid) and Zn(4-apa) (2), have been hydrothermally synthesized and characterized by elemental analysis, IR and single-crystal and powder X-ray diffraction. Crystal data for 1: monoclinic, space group C2/c with a = 23.056(5), b = 5.4224(11), c = 15.027(3) , β = 121.22(3)°, V = 1606.6(6) ?3, Dc = 2.468 g·cm-3, F(000) = 1168, μ = 7.122 mm-1, Z = 8, the final R = 0.0309 and wR = 0.0752 for 1763 observed reflections with I > 2σ(I). For 2: monoclinic, space group P21/c with a = 8.7852(18), b = 9.2744(19), c = 9.752(2) , β = 103.45(3)°, V = 772.7(3)3, Dc = 2.410 g·cm-3, F(000) = 544, μ = 7.387 mm-1, Z = 4, the final R = 0.0321 and wR = 0.0741 for 1696 observed reflections with I > 2σ(I). The structure of 1 shows a two-dimensional (4,4)-network composed of an inorganic ladder chain bridged by the phenyl-linkers of 4-apa ligands. Compound 2 exhibits a 3D layer-pillared framework with crb net, in which inorganic (4-82)-networks are joined by the phenyl-linkers.     

Blue Luminescent Zinc(II)-and Cadmium(II)-1,4-phenylenediacetate Complexes

1 INTRODUCTION The crystal engineering and design of solid-state coordination polymers have become a very attrac- tive field in recent years[1～4]. Many interesting fra- meworks with intriguing potential applications have been obtained through the self-assembly of selected metal centers and carboxylate ligands[5, 6]. Compared with aromatic carboxylate ligands such as terephtha- lic acid[7, 8], benzene tricarboxylic acid[9, 10], benzene tetracarboxylic acid[11, 12] and so on, those ligands …     

Syntheses and Crystal Structures of Two New One-dimensional Double Hydrogen-bonding-chain Complexes [Ni(bipy)_2Cl]·ClO_4 and [Zn(bipy)_2Cl]·BF_4

Two new transition metal complexes, [Ni(bipy)2Cl]·ClO4 (bipy = 2,2'-bipyridine) 1 and [Zn(bipy)2Cl]·BF4 2, have been synthesized and characterized by single-crystal X-ray diffraction analysis. Both 1 and 2 crystallize in monoclinic space group P21/n with Z = 4. For 1, a = 10.776(1), b = 12.067(1), c = 16.146(2) , β = 93.021(2)o, V = 2031.9(4) 3, Mr = 505.98, Dc = 1.654 g/cm3, μ = 1.255 mm–1, F(000) = 1032, the final R = 0.0406 and wR = 0.1002 for 3983 observed reflections with I > 2σ(I). For 2, a = 10.758(4), b = 12.058(4), c = 16.135(5) , β = 104.57(1)o, V = 2025.7(12) 3, Mr = 500.00, Dc = 1.639 g/cm3, μ = 1.396 mm–1, F(000) = 1008, the final R = 0.0470 and wR = 0.1237 for 3759 observed reflections with I > 2σ(I). The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. A one-dimen-sional zigzag double hydrogen-bonding-chain is generated by the intermolecular M-bipy ···anion···bipy- M hydrogen bonding interactions between the chelating ligands of bipy and anion.     

Synthesis and Characterization of Nickel(II) and Copper(II) Complexes with Schiff Base (1R,2R)-(-)-Diaminocyclohexane-N,N'-bis(3-tert-butyl-5-(4'-benzoic acid)-salicylidene)

Two homochiral metallosalen complexes, Ni(salen) (salen = (1R,2R)-(-)-diaminocyclohexane-N,N'-bis(3-tert-butyl-5-(4'-benzoic acid)-salicylidene) 1 and Cu(salen) 2, have been synthesized and characterized by IR, microanalysis, TGA, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 4. For 1, a = 12.082(2), b = 15.447(3), c = 18.784(4) , V = 3505.7(12) 3, Mr = 731.50, Dc = 1.386 g/cm3, μ = 0.606 mm–1, F(000) = 1544, the final GOOF = 1.043, R = 0.0496 and wR = 0.1248 for 4791 observed reflections with I > 2σ(I). For 2, a = 12.181(2), b = 15.501(3), c = 18.877(4) , V = 3564.3(12) 3, Mr = 736.33, Dc = 1.372 g/cm3, μ = 0.665 mm–1, F(000) = 1548, the final GOOF = 1.062, R = 0.0575 and wR = 0.1508 for 4562 observed reflections with I > 2σ(I). The crystal structures of 1 and 2 are isostructural with very similar supramolecular structures. An infinite two-dimensional network is generated by hydrogen bonding interactions and intermolecular π···π interactions.     

Synthesis and Crystal Structure of 9-（4-Dimethylaminophenyl）-l,8-dioxo- 9H-dibenzo [c,h ]-2,7,10-trioxanthene

The title compound 9-(4-dimethylaminophenyl)-1,8-dioxo-9H-dibenzo[c,h]- 2,7,10-trioxanthene (3) was synthesized by the reaction of 4-hydroxycoumarin with 4-dimethyla- minobenzaldehyde, and its chemical structure was determined by X-ray single-crystal diffraction. It crystallizes in triclinic, space group P with a = 7.8753(16), b = 11.029(2), c = 12.913(3) , α = 69.79(3), β = 89.01(3), γ = 81.90(3)°, V = 1041.5(4) 3, Z = 2 , F(000) = 456, Dc = 1.395 Mg/m3, Mr = 437.43, μ = 0.097 mm-1, λ = 0.71073 , the final R = 0.0491 and wR = 0.1314 for 2662 observed reflections with I > 2σ(I).     

Synthesis and Crystal Structure of Di-μ_(1,1)-azido-bis((azido)[N-ethyl-N'-(1-pyridin-2-ylmethylidene)ethane-1,2-diamino]cadmium(Ⅱ))

The dinuclear Schiff base cadmium(II) complex [Cd2(C10H15N3)2(N3)2 (μ1,1-N3)2] was prepared and characterized by elemental analysis, IR spectrum, and single-crystal X-ray dif- fraction. The crystal belongs to the monoclinic system, space group P21/n with a = 10.819(2), b = 11.058(2), c = 12.766(3) , β = 102.456(2)o, V = 1491.3(7) 3, Z = 2, Dc = 1.665 g/cm3, Mr = 747.42, λ(MoKα) = 0.71073 , μ = 1.470 mm-1, F(000) = 744, R = 0.0307 and wR = 0.0584. A total of 3420 unique reflections were collected, of which 2575 with I > 2σ(I) were observed. There is a crystallographic inversion centre at the midpoint of the two metal atoms in the complex. Each CdII atom in the complex is in a distorted octahedral coordination. The molecules in the crystal are linked through the intermolecular hydrogen bonds of N–H···N and C–H···N, forming a three- dimensional network.     

Synthesis and Structural Characterization of a Ruthenium Complex:trans-RuCl_2(COD)Py_2

A new ruthenium complex trans-RuCl2(COD)Py2 has been synthesized and charac- terized by elemental analysis, IR, 1H NMR and single-crystal X-ray diffraction. Crystal data: trans- RuCl2(COD)Py2, Mr = 438.35, monoclinic, space group P21/c, a = 8.9116(9), b = 14.6175(15), c = 13.7582(14) , β = 101.994(1)°, V = 1753.1(3) 3, Z = 4, Dc = 1.661 g/cm3 , F(000) = 888, μ = 1.199 mm-1, R = 0.0376 and wR = 0.0789 for 2492 observed reflections with I > 2σ(I).     

Syntheses, Crystal Structures and Properties of Two Supramolecules Assembled from Weak Interactions

Two complexes, [Cu2(Htdb)4(H2O)2] (1) and [Cd(bipy)2(Hmcmbc)2] (2) (H2tdb = 2,2-thiodibenzoic acid, H2mcmbc = m-(carboxyl-methyloxy)-benzenecarboxylic acid, bipy = 4,4'-bipyridine), have been prepared, and were characterized by elemental analysis, FT-IR and single-crystal X-ray diffraction. Structures indicate that complex 1 is a single molecule, and 2 is a one-dimensional chain. Their two-and three-dimensional frameworks are constructed through hydrogen bonding, π…π or C–H…π stacking, and such other weak interactions. The cyclic voltametric behavior of complex 1 and luminescence property of complex 2 were investigated. 1 belongs to the triclinic system, space group P with a = 7.8607(6), b = 11.7619(9), c = 15.3481(12) , α = 109.3670(10), β = 92.4420(10), γ = 92.0450(10)°, V = 1335.65(18) 3, Mr = 1256.26, Dc = 1.5619(2) g/cm3, F(000) = 642, μ = 1.029 mm–1, Z = 1, the final R = 0.0289 and wR = 0.0763 for 5199 observed reflections with I > 2σ(I). Complex 2 crystallizes in triclinic, space group P with a = 9.6378(10), b = 9.7508(10), c = 19.055(2) , α = 88.7020(10), β = 80.5260(10), γ = 69.2000(10)o, V = 1649.9(3) 3, Mr = 815.07, Dc = 1.641 g/cm3, μ = 0.732 mm-1, F(000) = 828, Z = 2, the final R = 0.0511 and wR = 0.1149 for 4729 observed reflections (I > 2σ(I)).     

Synthesis and Characterization of Chiral Mercury（II） and Cadmium（II） Complexes with 3,3＇-Bipyridine-5,5＇,6,6＇-tetramethyl-2,2＇-dimethoxy-1,1＇-biphenyl

Two homochiral mercury (1) and cadmium (2) complexes derived from chiral twisted biphenyl pyridine ligand (3,3'-bipyridine-5,5',6,6'-tetramethyl-2,2'-dimethoxy-1,1'-biphenyl) have been synthesized and characterized by IR, microanalysis, TGA, UV-Vis, powder and single-crystal X-ray crystallography. Both 1 and 2 crystallize in orthorhombic space group P21212 with Z = 2. For 1, a = 14.2038(16), b = 14.3630(17), c = 7.0257(8), V = 1433.3(3)3, Mr = 878.91, Dc = 2.037 g/cm3, μ = 7.549 mm-1, F(000) = 824, the final GOF = 1.017, R = 0.0296 and wR = 0.0645 for 2925 observed reflections with I > 2σ(I). For 2, a = 14.212(3), b = 14.392(3), c = 7.0498(14), V = 1442.0(5)3, Mr = 790.72, Dc = 1.821 g/cm3, μ = 2.924 mm-1, F(000) = 760, the final GOF = 1.075, R = 0.0340 and wR = 0.0834 for 3144 observed reflections with I > 2σ(I). The crystal structures of 1 and 2 are isostructural and each adopts a two-dimensional supramolecular network which contains the C-H···π interactions.     

Synthesis and Crystal Structure of a Coordination Polymer {[Co(phth)(phen)(H_2O)]·(C_2H_5OH)}_n

1 INTRODUCTION Metal-organic coordination polymer has particu- lar and special structure characters with some caves, holes and channels[1], and can be used in selected catalysis, molecular recognition, reversible exchan- ge of host-guest molecules (ions), super purity sepa- ration, biological conductor[2～5], etc. In the past ten years, polymers with bridging ligand have been widely investigated[6, 7]. The development of supra- molecular architectures of inorganic-organic hybrid molecules …     

Syntheses, Crystal Structures and Fluorescence Properties of Two Pb（II） 1-Naphthoate Complexes

Two new 1-naphthoate-based Pb(Ⅱ) complexes, [Pb(phen)(NA)2]n 1 and [Pb(bpp)(NA)2]n 2 (NA = 1-naphthoate, phen = 1,10-phenanthroline, and bpp = 1,3-bi(4-pyri- dyl)propane), were hydrothermally synthesized and structurally characterized. 1 is of monoclinic system, space group C2/c with a = 28.114(3), b = 10.9601(10), c = 8.6843(8) , β = 93.3760(10)°, V = 2671.3(4) 3, Dc = 1.814 g/cm3, Mr = 729.73, Z = 4, F(000) = 1416, μ = 6.360 mm-1, the final R = 0.0346 and wR = 0.0948 for 2184 observed reflections with I > 2σ(I). Complex 2 crystallizes in monoclinic, space group C2/c with a = 26.491(2), b = 8.7773(6), c = 27.893(2) , β = 113.3020(10)°, V = 5956.8(8)3, Dc = 1.668 g/cm3, Mr = 747.78, Z = 8, F(000) = 2928, μ = 5.706 mm-1, the final R = 0.0211 and wR = 0.0493 for 3677 observed reflections with I > 2σ(I). Both complexes present one-dimensional (1-D) zigzag chains extended by anionic NA linkers for 1 and bridged by neutral bpp connectors for 2, which are further aggregated into 2-D supramolecular networks by interchain π···π stacking interactions. In addition, the two solid-state complexes exhibit different strong emissions at room temperature, suggesting their potential applications as fluorescence materials.     

Synthesis and Crystal Structure of 3,3＇-（4-Dimethylaminobenzylidene）- bis-（4-hydroxycoumarin）

The title compound 3,3'-(4-dimethylaminobenzylidene)-bis-(4-hydroxycoumarin) 3 was synthesized by the reaction of 4-hydroxycoumarin with 4-dimethylaminobenzaldehyde, and its chemical structure was determined by X-ray single-crystal diffraction. It crystallizes in monoclinic, space group P21/n with a = 11.698(2), b = 10.882(2), c = 16.594(3) , β = 90.69(3)o, V = 2112.1(7) 3, Z = 4, F(000) = 952, Dc = 1.432 Mg/m3, Mr = 455.45, μ = 0.102 mm-1, λ = 0.71073 , the final R = 0.0779 and wR = 0.2143 for 3031 observed reflections with I > 2σ(I).     

Syntheses and Crystal Structures of Two New Macrocyclic Compounds

Two new macrocyclic compounds, [Cu2(L)2](ClO4)4·2CH3OH (1) and [Cu(L)](ClO4)2·2H2O (2) (L = 1,3,10,12,15,18-hexaazatetracyclodocosane) were synthesized by condensation reactions involving amines and formaldehyde in the presence of copper anion. Compound 1 crystallizes in triclinic, space group Pí with a = 10.442(2), b = 14.197(3), c = 17.388(4), α = 91.218(4), β = 90.69(3), γ = 93.756(4)o, V = 2520.4(9)3, Z = 2, F(000) = 1260, Dc = 1.589 Mg/m3, Mr = 1205.92, μ = 1.137 mm-1, λ = 0.71073, the final R = 0.0668 and wR = 0.1573 for 9703 observed reflections with I > 2σ(I). Compound 2 crystallizes in monoclinic, space group C2/c with a = 16.911(2), b = 11.4172(15), c = 27.059(4), β = 107.787(2)o, V = 4974.7(12)3, Z = 8, F(000) = 2504, Dc = 1.610 Mg/m3, Mr = 602.92, μ = 1.155 mm-1, λ = 0.71073 , the final R = 0.0419 and wR = 0.1131 for 4374 observed reflections with I > 2σ(I).     

Synthesis and Crystal Structure of a Cobalt（Ⅱ） Coordination Polymer with Benzene-1,3,5-triacetate and 1,2-Di（pyridin-4-yl）ethene

A novel coordination polymer, [Co3(bta)2(dpe)3(H2O)2]·2H2O (1, H3bta = benzene-1,3,5-triacetic acid, and dpe = 1,2-di(pyridin-4-yl)ethene), has been hydrothermally prepared and characterized by IR spectroscopy, elemental analysis and single-crystal X-ray diffraction. The crystal is of triclinic system, space group P , with a = 9.5687(15), b = 11.2470(17), c = 13.686(2) , α = 78.262(3), β = 89.271(4), γ = 81.292(3)°, V = 1425.2(4) 3, C60H56N6O16Co3, Mr = 1293.90, Dc = 1.508 g/cm3, F(000) = 667, μ = 0.940 mm-1 and Z = 1. The final R = 0.0707 and wR = 0.1413 for 4950 observed reflections (I > 2σ(I)). In the title complex, the bta ligand acts as a four-dentate bridging ligand to link up cobalt atoms into lamellar frameworks which are further interlinked by the dpe ligands to generate a trinodal (3,4,6)-connected (4.62)2(42.68.83.102)(64.82) net.     

Novel Copper（Ⅱ） and Zinc（Ⅱ） 2-D Supramolecular Structures Based on Carboxylate and 1-Substitutedimidazole Mixed-ligands

Using the ligand bis(3-(1H-imidazol-1-yl)-1-phenylpropan-1-one) L, two novel com- plexes [CuL2(ph))]·H2O 1 and [ZnL2(tp)] 2 (ph = phthalic acid, tp = terephthalic acid) have been synthesized and their crystal structures were determined by single-crystal X-ray diffraction analysis. Crystal data for 1: triclinic, space group P1, a = 9.4300(17), b = 12.148(2), c = 13.721(2) , α = 109.620(2), β = 94.351(2), γ = 94.830(2)°, C32H30N4O7Cu, Mr = 646.14, V = 1466.2(4) 3, Z = 2, Dc = 1.464 g/cm3, μ(MoKα) = 0.801 mm-1, F(000) = 670, the final R = 0.0337 and wR = 0.0859 for 5122 observed reflections with I > 2σ(I). And those for 2: monoclinic, space group P2/n, a = 7.1866(11), b = 14.144(2), c = 14.407(2) , β = 101.427(2)°, C32H28N4O6Zn, Mr = 629.95, V = 1435.4(4) 3, Z = 2, Dc = 1.457 g/cm3, μ(MoKα) = 0.908 mm-1, F(000) = 652, the final R = 0.0438 and wR = 0.0821 for 2546 observed reflections with I > 2σ(I). In 1 and 2, ph or tp ligands bridge the six-coordinated copper(II) or four-coordinated zinc(II) ions forming 1D zigzag chains while L ligands act as the terminal monodentate ligand. It is noted that weak non-classical C–H···O plays the important and dominating roles in the formation of 2D supramolecular architectures of 1, but in 2 non-classical C–H···O and aromatic π-π stacking interactions are quite important and play dominant roles in the self-assembly of 2D supramolecular architectures.     

Synthesis and Crystal Structure of the Binuclear Complex:[Cu_2(phen)_2(ip)(Hip)_2]·4H_2O

A binuclear complex [Cu2(phen)2(ip)(Hip)2]·4H2O has been synthesized by the reaction of Cu(CH3COO)2·H2O, phen(1,10-phenanthroline) and isophthalic acid (H2ip) under hydrothermal condition. Elemental analysis, IR spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure. Crystal data for this complex: mono- clinic, space group C2/c, a = 19.214(3), b = 10.6973(14), c = 22.567(3) , β = 105.081(2)°, C24H19N2O8Cu, Mr = 526.95, Z = 8, F(000) = 2160, V = 4478.6(10) 3, Dc = 1.563 g/cm3, μ = 1.030 mm-1, –24≤h≤16, –13≤k≤13, –28≤l≤28, R = 0.0369 and wR = 0.0819 for 4615 (Rint = 1.0357) independent reflections and 3290 observed ones (I > 2σ(I)). Structural analysis shows that coordination geometry of Cu(Ⅱ) is a planar square, and the title complex exhibits a 2-D framework supramolecular structure by hydrogen bonds and π-π stacking interactions.     

Synthesis and Crystal Structure of (9S)-2′-O-Benzoyl-9,11-[carbonylbis(oxy)]-9-deoxo-5-O-(β-D-desosaminyl)-12,21-anhydro-9-hydroxy-erythronolide A

The title compound (9S)-2′-O-benzoyl-9,11-[carbonylbis(oxy)]-9-deoxo-5-O-(-D-desosaminyl)-12,21-anhydro-9-hydroxyerythronolide A 1 was synthesized. The crystal structure of the acetone solvate of 1, C37H55NO11·C3H6O, was determined by single-crystal X-ray diffraction analysis. It belongs to monoclinic system, space group P21 with a = 14.4691(10), b = 8.2626(6), c = 17.5990(11) , β = 94.167(1)°, V = 2098.4(2)3, Mr = 748, Z = 2, Dc = 1.184 g/cm3, μ = 0.087 mm-1, F(000) = 808, S = 1.026, R = 0.0542 and wR = 0.1322 for 3331 observed reflections (I > 2σ(I)). In the solid state, molecules of 1 are linked into spirals along the b axis by O(25)- H(25)···O(29) intermolecular hydrogen bond.     

Hydrothermal Synthesis and Crystal Structure of a New One-dimensional Cobalt（Ⅱ） Complex with 2-Pyridinecarboxyic Acid and 4,4＇-Bipyridine Ligands

A new metal-organic coordination polymer [Co（2-pya）2（4,4＇-bipy）]2n-[（4,4＇- bipy）0.5· H2O]2n （2-pya = 2-pyridinecarboxylic acid, 4,4＇-bipy = 4,4＇-bipyridine） 1 has been hydrothermally synthesized and structurally characterized by elemental analysis, IR spectrum, TG and single-crystal X-ray diffraction. The complex crystallizes in tetragonal, space group I41/a with a = b = 22.719（2）, c = 10.710（2）/k, V = 5527.8（14） A3, C54H46N10Co2O10, Mr= 1112.87, Dc = 1.337 g/cm3,μ（MoKa） = 0.665 mm-1, F（000） = 2296, Z = 4, the final R = 0.0633 and wR = 0.1096 for 1261 observed reflections （I 〉 2σ（I））. It exhibits a one-dimensional chain-like structure constructed by mixed ligands of 2-pyridinedicarboxylic acid and 4,4＇-bipyridine.     

Synthesis,Structure,Electrochemistry and Fluorescence Properties of a One-dimensional Coordination Polymer {[Cd[μ-(4,4′-dps)]_2(H_2O)_2]·(4-abs)_2(H_2O)_2}_n

A new cadmium(II) compound, {[Cd[μ-(4,4'-dps)]2(H2O)2]·(4-abs)2(H2O)2}n 1 (4,4'-dps = 4,4'-dipyridylsulfide, 4-abs = deprotonated 4-amino benzenesulfonic acid), has been synthesized and structurally characterized. It belongs to the orthorhombic system, space group Pbcn with a = 19.950(3), b = 10.6381(13), c = 18.055(2) , V = 3831.8(8) 3, Z = 4, C32H36CdN6O10S4, Mr = 905.31, F(000) = 1848, μ = 0.850 mm-1, Dc = 1.569 Mg/m3 , the final R = 0.0238 and wR = 0.0589 for 3080 observed reflections with I > 2σ(I). Complex 1 is a one-dimensional linear chain coordination polymer and the repeat unit is comprised of doubly charged cadmium complex cation, uncoordinated 4-aminobenzene sulfonate anions and water molecules. The cadmium(II) ion adopts a six-coordinate distorted octahedral geometry. Complex 1 is stabilized and linked into a three-dimensional layered structure through intermolecular O–H···O and N–H···O hydrogen bonds together with electrostatic force. The cyclic voltammograms and fluorescence spectrum of 1 were also measured. It shows one irreversible redox process and emits a very strong and sharp fluorescent band at about 341 nm.     

Synthesis and Hydrogen-bonded Interpenetrating Grid Structure of 5,5＇-Bis [4- （2-hydroxyethyl）phenyl] diazo-dipyrromethane

A new 5,5'-bisdiazo-dipyrromethane compound 3 has been synthesized and cha- racterized. The crystal of 3 is of orthorhombic, space group Iba2 with a = 19.1914(17), b = 9.8396(8), c = 13.7643(12) , V = 2599.2(4)3, Z = 4, C29H34N6O2, Mr = 498.62, Dc = 1.274 g/cm3 , F(000) = 1064, μ(MoKα) = 0.083 mm-1, the final R = 0.0302 and wR = 0.0786 for 6361 observed reflections with I > 2σ(I), and R = 0.0320 and wR = 0.08006 for all data. It reveals that the molecules of compound 3 assemble into grid structures through a R22(7) type hydrogen bonding motif between azopyrrole and hydroxyl group. The grids interpenetrate each other with the assistance of C-H···π interaction.