Synthesis,Crystal Structure and Catalytic Activity of a Pd-PEPPSI Complex Bearing Bromine Group

A new Pd-PEPPSI complex(2) with the bromo groups on the para-positions of N-aryl moieties of NHC has been synthesized and characterized by NMR and X-ray single-crystal diffraction. Complex 2 crystallizes in monoclinic, space group P2_1/c with a = 11.8790(8), b = 14.3038(10), c = 15.9905(11) ?, β = 101.291(2)°, V = 2664.4(3) ?3, Z = 4, D_c = 1.722 Mg/m~3, μ = 3.913 mm~(-1), F(000) = 1352, the final R = 0.0682 and wR = 0.1914 for 15113 observed reflections(I 2σ(I)), R(all data) = 0.0970, w R(all data) = 0.2115, completeness to theta of 25.00 is 100.0% and GOOF = 1.035. Influenced by the electron-withdrawing bromo groups, the Pd-PEPPSI complex(2) showed high catalytic activity for the Suzuki-Miyaura cross-coupling reactions of aryl chlorides and arylboronic acids with a low catalyst loading(0.05 mol%) at room temperature in air.     

Two Coordination Novel Polymers Based on a Flexible Ligand N,N?-diacetic Acid Imidazolium

{[Cu_3(cis-DAM)_4(OH)_2]·12H_2O}_n 1 and [Ag_3(trans-DAM)_2(NO_3)]_n 2 with a flexible ligand N,N?-diacetic acid imidazolium(HDAM) were synthesized and characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the orthorhombic I222 space group with a = 12.033(2),b = 12.498(3),c = 14.963(3) ?,V = 2250.4(8) ?~3,Z = 8,C_7H_(13.5)N_2O_(7.5)Cu_(0.75),M_r = 293.35,D_c = 1.732 g·cm~(-3),F(000) = 1210,GOF = 1.087,the final R(I 2σ(I)) = 0.0521 and w R(all data) = 0.1386. Compound 2 crystallizes in the monoclinic C2/c space group with a = 21.601(4),b = 8.321(2),c = 13.589(3) ?,β = 126.95(3)°,V = 1951.9(7) ?~3,Z = 8,C_7H_7N_(2.5)O_(5.5)Ag_(1.5),M_r = 375.96,D_c = 2.559 g·cm~(-3),F(000) = 1448,GOF = 1.017,R(I 2σ(I)) = 0.0222 and w R(all data) = 0.0633. Compound 1 displays a novel 2D layer,consisting of a couple of left-helical chains with a pitch of 12.498(3) ? formed by μ_3-cis-DAM~– ligands and Cu(1) ions,which are stabilized by hydrogen bonding interactions to give a 3D supramolecular framework. As for 2,Ag(1) ions are doubly bridged by trans-DAM~– and NO_3~– to form [Ag(1)_2O_4] chains,which are further connected by Ag(2) and trans-DAM~– to build a 3D framework. Additionally,thermogravimetric analyses,FT-IR spectroscopy,UV-visible spectroscopy,and the fluorescent properties were discussed.     

New Efficient Copper(Ⅱ)-catalyzed Direct Access to Primary Amide from Aldehyde under Solvothermal Condition and Related Crystal Structure Study

Two 1-methyl-1H-benzo[d]imidazole derivatives, C_(18)H_(14)CuN_4O_4·C_4H_8O_2(1) and C_9H_9N_3O(2), have been synthesized and characterized by NMR, MS, FT-IR, elementary analysis and X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group P2_1/n with a = 9.6888(3), b = 7.3772(2), c = 14.3277(4) ?, β = 95.819(3)°, V = 1018.81(5) ?~3, M_r = 501.98, Z = 2, D_c = 1.636 g/cm~3, F(000) = 518, μ = 1.123 mm~(-1), MoKα radiation(λ = 0.71073 ?), the final R = 0.0325 and wR = 0.0859 for 1821 observed reflections with I 2σ(I). Compound 2 crystallizes in monoclinic, space group C2/c with a = 14.2908(14), b = 14.4268(13), c = 8.4802(6) ?, β = 108.513(9)o, V = 1657.9(3) ?~3, M_r = 175.19, Z = 8, D_c = 1.404 g/cm~3, F(000) = 736, μ = 0.097 mm~(-1), Mo Kα radiation(λ = 0.71073 ?), the final R = 0.0563 and wR = 0.1531 for 1231 observed reflections with I 2σ(I). Intermolecular(N-H···N, N-H···O) and intramolecular(N-H···N, C-H···O) hydrogen bonds, as well as C-H···π and π-π stacking interactions, help to stabilize the crystal structure of compound 2.     

Synthesis,Characterization and Luminescent Properties of Two Copper(Ⅰ) Complexes Based on 2,2?-Biquinoline and Phosphorous Ligand

Three new copper(Ⅰ) complexes, namely [Cu(DPEphos)(Biq)]CF_3SO_3(1) and [Cu(PPh_3)_2(Biq)]CF_3SO_3(2) and [Cu(PPh_3)_2(Biq)]ClO_4(3)(DPEphos = bis[2-(diphenylphosp hino)phenyl]ether, PPh_3 = triphenylphosphine and Biq = 2,2?-biquinoline), are synthesized and characterized by IR, ~1H NMR, ~(31) P NMR, fluorescence spectra and terahertz time-domain spectroscopy(THz-TDS). Complex 1 crystallizes in triclinic, space group P1 with a = 12.6997(5), b = 13.2813(5), c = 15.3593(6) ?, α = 80.211(3)°, β = 88.752(3)°, γ = 70.113(3)°, V = 2398.85(15) ?~3, C_(55)H_(41.2)CuF_3N_2O_(4.6)P_2S, Mr = 1018.27, Z = 2, Dc = 1.410 g/cm3, F(000) = 1048, μ = 0.628 mm-1, the final R = 0.0450 and w R = 0.1105 for 9419 observed reflections(I 2σ(I)). Complex 2 crystallizes in monoclinic, space group C2/c with a = 19.9961(7), b = 15.9774(5), c = 17.7908(6) ?, β = 119.758(4)°, V = 4982.8(3) ?~3, C_(56.47)H_(47.88)CuF_3N_2O_(4.47)P_2S, Mr = 1040.54, Z = 4, Dc = 1.387 g/cm~3, F(000) = 2154, μ = 0.606 mm-1, the final R = 0.0430 and w R = 0.1218 for 4897 observed reflections(I 2σ(I)). Complex 3 crystallizes in monoclinic, space group C2/c with a = 19.7534(8), b = 15.0797(5), c = 17.8097(7) ?, β = 116.400(5)°, V = 4751.8(3) ?~3, C_(56)H_(45)ClCuN_3O_4P_2, Mr = 984.88, Z = 4, Dc = 1.377 g/cm~3, F(000) = 2040, μ = 0.635 mm-1, the final R = 0.0731 and w R = 0.2180 for 4670 observed reflections(I 2σ(I)). In the emission spectra, shifts of emission peak are derived from ligand-centered(π-π*) transition.     

Syntheses,Structures,and Luminescent Properties of Zinc(Ⅱ) and Silver(Ⅰ) Complexes Based on 1-(4?-Carboxylatobenzyl)-3-(pyrazin-2-yl)pyrazole

Two novel coordination compounds, [Zn(CBPP)2(H2O)2]·3H2O(1) and[Ag(CBPP)·2H2O](2)(HCBPP = 1-(4?-carboxylatobenzyl)-3-(pyrazin-2-yl)pyrazole), were hydrothermally synthesized and characterized. Compound 1 crystallizes in monoclinic, space group C2 with a = 26.221(4), b = 8.4211(7), c = 14.295(3) ?, β = 114.561(8)o, V = 2705.9(2) ?3, Dc = 1.587 g/cm3, C28H28Cl2N8O9 Zn, Mr = 685.97 F(000) = 1416, μ(Mo Kα) = 0.926 mm-1, Z = 4, R = 0.0287, w R = 0.1076 for 2818 observed reflections(I 2σ(I)), and R = 0.0300, w R = 0.1110 for all data. In 1, each deprotonated CBPP-ligand with a bidentate coordination mode connects two Zn(II) atoms to generate a 1D helical chain along the b axis. The adjacent chains intersect with each other through hinged Zn(II) ions to build up an interesting two-dimensional network. Compound 2 crystallizes in monoclinic, space group P21/n with a = 6.3544(1), b = 11.7195(3), c = 19.3188(4) ?, β = 94.297(2)o, V = 1434.64(5) ?3, Dc = 1.894 g/cm3, C14H13 Ag N4O4, Mr = 409.15 F(000) = 816, μ(Mo Kα) = 11.536 mm-1, Z = 4, R = 0.0456 and w R = 0.1184 for 2402 observed reflections(I 2σ(I)), and R = 0.0517, w R = 0.1275 for all data. In 2, each ligand binds two Ag(I) atoms in a tridentate coordination mode to form an infinite zigzag chain. Their thermal and photoluminescent properties were also investigated.     

Crystal Structures,Luminescent Properties and Hirshfeld Surface Analyses of Zn(Ⅱ) and Cd(Ⅱ) Compounds Based on 1-(2-Carboxyl-phenyl)-3-(pyridin-2-yl)pyrazole

Two compounds,[Zn_2(Hcppp)_2(cppp)_2(H_2O)_2]·2 NO_3·6 H_2O(1) and [Cd(Hcppp)_2Cl_2]· 3H_2O(2)(Hcppp = 1-(2-carboxyl-phenyl)-3-(pyridin-2-yl)pyrazole),are synthesized and characterized by IR,TGA and X-ray single-crystal/powder diffraction.Compound 1 crystallizes in monoclinic system,space group P2_1/c with a = 9.894(2),b = 15.856(3),c = 20.430(4) ?,β = 101.70(3)°,V = 3138.5(11) ?~3,Z = 2,M_r = 1457.94,D_c = 1.543 g/cm~3,F(000) = 1504,R = 0.0278 and wR = 0.0749 for 6157 observed reflections(I 2σ(I)).Compound 2 crystallizes in triclinic system,space group P1 with a = 9.1424(4),b = 11.6427(5),c = 16.1345(7) ?,α = 102.6430(10)°,β = 95.4530(10)°,γ = 104.0060(10)°,V = 1605.94(12) ?~3,Z = 2,M_r = 767.88,D_c = 1.588 g/cm~3,F(000) = 776,R = 0.0307 and wR = 0.0764 for 6275 observed reflections(I 2σ(I)).Compound 1 exhibits a binuclear structure while compound 2 shows a mononuclear structure.In compound 1,two cppp-ligands display the μ_2-kN,N′:k O and two Hcppp ligands show the μ_1-kN,N′ coordination modes.However,two Hcppp ligands connect one Cd(Ⅱ) cation and exhibit the μ_1-kN,N′ binding mode in compound 2.The compounds are both studied using Hirshfeld surface analyses and 2D fingerprint plots.The luminescent properties are also discussed.     

Silver(Ⅰ) Complexes with Mixed Diphosphine Ligands:Syntheses,Characterization and Spectroscopic Properties

Two novel silver(I) complexes [Ag(DPEphos)(dppe)]Cl O4(1) and [Ag(DPEphos)-(dppe)]SCN(2)(DPEphos = bis[2-(diphenylphosphino)phenyl]ether, dppe = bis(diphenylphosphino)ethane) are synthesized and characterized by IR, 1H/31 P NMR spectroscopy and fluorescence spectra. Complex 1 crystallizes in monoclinic, space group P21/c with a = 14.8821(12), b = 12.6620(11), c = 36.025(3) ?, β = 112.633(2)°, V = 6265.7(9) ?3, C62H52 Cl O5P4Ag, Mr = 1144.24, Z = 4, Dc = 1.213 g/cm3, F(000) = 2352, μ = 0.510 mm-1, the final R = 0.0616 and w R = 0.1192 for 4003 observed reflections(I 2σ(I)). Complex 2 crystallizes in monoclinic, space group P21/c with a = 14.9021(13), b = 12.6100(11), c = 35.920(3) ?, β = 112.852(2)°, V = 6220.2(9) ?3, C63H52NOP4 SAg, Mr = 1102.87, Z = 4, Dc = 1.178 g/cm3, F(000) = 2272, μ = 0.498 mm-1, the final R = 0.0912 and w R = 0.1706 for 3287 observed reflections(I 2σ(I)). In mono-nuclear complexes 1 and 2, the Ag(I) atom is chelated by DPEphos and dppe ligand. In the 31 P NMR spectra, there are splitting signals(doublets or triplets) which can be attributed to the coupling of the 107,109Ag–31P(from DPEphos or dppe ligand). All the emission peaks of these complexes are attributed to ligand-centered(π-π*) transitions.     

Synthesis,Crystal Structure and Biological Activity of Dimethyl 1-Methyl-1,4-dihydroquinoline-3,4-dicarboxylate and Tetramethyl Pyrrolo-[1,2-a]quinoline-2,3,4,5-tetracarboxylate

The target compounds 3(C_(14)H_(15)NO_4) and 4(C_(20)H_(17)NO_8) were synthesized and structurally determined by single-crystal X-ray diffraction. The crystal of 3 is in the monoclinic system, space group P2_1/c with a = 7.3017(3), b = 7.8737(5), c = 22.4227(11) ?, β = 94.837(5)°, C_(14)H_(15)NO_4, M_r = 261.27, D_c = 1.351 g/cm~3, V = 1284.51(11) ?3, Z = 4, F(000) = 552, μ(MoKa) = 0.828 mm~(–1), T = 289.12(10) K, 2236 independent reflections with 1827 observed ones(I 2σ(I)), R = 0.0515 and w R = 0.1394 with GOF = 1.044(R = 0.0605 and w R = 0.1548 for all data). The crystal of compound 4 is in the monoclinic system, space group P21/c with a = 7.1269(3), b = 12.6518(6), c = 20.7540(8) ?, β = 96.941(4)°, C_(20)H_(17)NO_8, M_r = 399.35, D_c = 1.428 g/cm~3, V = 1857.61(14) ?3, Z = 4, F(000) = 832.0, μ(MoKa) = 0.950 mm~(–1), T = 288.81(10) K, 3216 independent reflections with 2253 observed ones(I 2σ(I)), R = 0.0612 and wR = 0.1548 with GOF = 1.055(R = 0.0824 and w R = 0.1790 for all data). The skeleton of 1,4-dihydroquinoline 3 is noncoplanar, while pyrrolo[1,2-a]-quinoline 4 owns a coplanar frame structure. One-dimensional interaction model of compound 4 was formed by the one kind of π-π interaction between the two adjacent molecules at upper and lower levels. And the inhibition to the strand transfer process of HIV-1 integrase of the title compounds was also evaluated.     

Pyridine-contained α-Cyanostilbenzene Schiff Base:Preparation,Crystal Structure and Photoluminescence

A novel pyridine-contained α-cyanostilbenzene Schiff base,(Z)-3-(4-butoxyphenyl)-2-(4-((E)-pyridin-2-yl-methyleneamino)phenyl)acrylonitrile(L), has been synthesized and characterized by 1H NMR, 13 C NMR, FT-IR spectra and single-crystal X-ray diffraction.Single-crystal data show that compound L belongs to the triclinic system, space group P1, with a =8.759(4), b = 10.779(4), c = 12.594(5) A, α = 65.873(4), β= 88.332(5), γ= 73.800(5)°, Mr= 381.46,V = 1037.2(7) A3, Z = 2, D= 1.221 g/cm-3, μ = 0.076 mm-1c, F(000) = 404, Rint = 0.0311, R(I 2σ(I)) = 0.0484, w R(I 2σ(I)) = 0.1544, R(all data) = 0.0484, w R(all data) = 0.1692,completeness to theta = 25.000 being 99.0% and GOF = 1.179. There are two kinds of intermolecular hydrogen bonds and one kind of C–H···π weak interaction between adjacent molecules. Compound L can be used as a candidate for desirable devices with high performance due to its good thermal stability and excellent optical performance.     

Two Co(Ⅱ) Coordination Polymers Based on 3,5-Di(4H-1,2,4-triazole-4-yl)benzoic Acid Ligand: Syntheses,Structures and Magnetic Property

Two Co(Ⅱ) coordination polymers, namely [Co(L)Cl]_n(1) and [Co(L)(CH_3 COO)]_n(2), {HL = 3,5-di(4 H-1,2,4-triazole-4-yl)benzoic acid}, were synthesized under hydrothermal conditions. Compound 1 crystallizes in orthorhombic system, space group Pmma with a = 7.032(5), b = 11.555(8), c = 8.185(5) ?, V = 665.1(7) ?~3, Z = 2, Dc = 1.746 g/cm3~, F(000) = 350, Mr = 349.61, μ = 1.504 mm~(-1), the final R = 0.0568 and w R = 0.1739 for 2312 observed reflections with I 2σ(I). Compound 2 crystallizes in orthorhombic system, space group Pmma with a = 7.7505(17), b = 11.391(3), c = 8.0298(18) ?, V = 708.9(3) ?~3, Z = 2, Dc = 1.748 g/cm~3, F(000) = 378, Mr = 373.20, μ = 1.245 mm-1, the final R = 0.0350 and w R = 0.0873 for 5239 observed reflections with I 2σ(I). Single-crystal X-ray analyses revealed that complexes 1 and 2 exhibit similar 2 D layer structures with uncoordinated carboxyl as dangling arms. The neighboring layers are further connected by these arms, leading to interest 2 D → 3 D polythreading frameworks. Moreover, the magnetic susceptibility study indicates compound 1 exhibits antiferromagnetic behavior.     

Synthesis,Structure and Photoelectric Property of a 3D Supramolecular Zinc Coordination Polymer

Using a rigid azo ligand 4-[(8-hydroxy-5-quinolinyl)azo]-benzoic acid(H2 L),a new supramolecular compound [Zn(L)(H_2O)_2]_n(1) has been solvothermally synthesized and structurally characterized by X-ray single-crystal diffraction,infrared spectrum,elemental analysis,power X-ray diffraction and thermal analysis.Compound 1 crystallizes in monoclinic,space group C2/c with a = 30.372(8),b = 11.415(3),c = 9.248(3) ?,β = 106.94(3)o,V = 3067.20(15) ?3,C_(16)H_(13)N_3O_5Zn,M_r = 392.66,Z = 8,D_c = 1.701 Mg/m~3; F(000) = 1600,μ = 1.636 mm~(-1),reflections collected:7290,reflections unique:2735,R_(int)= 0.0282,R = 0.0351,wR(all data) = 0.0919,GOOF on F~2 = 1.036.Compound 1 exhibits a one-dimensional(1 D) zig-zag chain structure connected into a three-dimensional(3D) supramolecular network through hydrogen bonding interactions.Fluorescent property and electrochemical property were detected on compound 1.     

Synthesis,Structure and Photocatalytic Activity of Two 4-(2,6-Di(pyrazin-2-yl)pyridin-4-yl)benzoate-Based Chain Complexes

Two new one-dimensional chains extended by alternate benzenedicarboxylate(BDC) and 4-(2,6-di(pyrazin-2-yl)pyridin-4-yl)benzoate(L~-) connectors, {[Cu(L)(BDC)_(0.5)]·3.5 H_2 O}_n (1) and {[Zn(L)(BDC)_(0.5)] ·H_2 O}_n (2), were solvothermally synthesized. Complex 1 is in triclinic system, space group P1 with a = 9.6456(14), b = 11.1160(16), c = 12.0414(18) ?, α = 106.266(3), β = 92.277(3), γ =108.104(3)°, V = 1166.6(3) ?~3, D_c = 1.603 g·cm~(-3), Mr = 563.00, Z = 2, F(000) = 578, μ = 0.996 mm~(-1), the final R = 0.0575 and wR = 0.1386 for 3704 observed reflections with I 2σ(I). Complex 2 crystallizes in monoclinic, space group C2/c with a = 28.607(5), b = 8.9767(16), c = 19.705(4) ?, β = 125.396(3)°, V = 4125.0(13) ?~3, D_c = 1.674 g·cm~(-3), Mr = 519.79, Z = 8, F(000) = 2120, μ = 1.242 mm~(-1), the final R = 0.0487 and w R = 0.0907 for 2944 observed reflections with I 2σ(I). Resulting from the narrower band gap and broader response to visible light, the CuII-chain exhibits better photocatalytic performance towards the degradation of rhodamine B and methylene blue than those of ZnII-chain.     

Syntheses,Structures and Luminescent Properties of the Cadmium(Ⅱ) Complex with 3,3?-Thiodipropionic Acid

One new luminescent material of complex {[Cd(DPA)(H_2O)_2]·(H_2O)_2}_n(1) was synthesized by evaporation methods using 3,3?-thiodipropionic acid(DPA) and cadmium nitrate as the starting materials. Compound 1 crystallizes in the monoclinic system,space group P2_1/n with a = 7.5460(7),b = 13.372(3),c = 12.304(3) ?,β = 95.95(3)o,V = 1234.8(4) ?~3,D_c = 1.940 g/cm~3,C_6H_(16)O_8 SCd,M_r = 360.65,F(000) = 720,μ(Mo Ka) = 1.960 mm~(-1),Z = 4,R = 0.0460 and wR = 0.1185 for 1835 observed reflections(I 2σ(I)),and R = 0.0591,wR = 0.1245 for all data. The complex has been characterized by elemental analysis,FT-IR,TG,PXRD and X-ray single-crystal structure analysis and the fluorescence property has also been studied. As a result,complex 1 possesses a two-dimensional(2-D) structure through DPA ligands interconnecting Cd2+ ions. Complex 1 emits the intense fluorescence of 420 nm in the solid state at room temperature.     

Synthesis,Crystal Structure and Photophysical Property of 4-(9-Oxoacridin-10(9H)-yl) Benzonitrile

A purely organic compound, 4-(9-oxoacridin-10(9 H)-yl) benzonitrile(1), was synthesized and characterized by NMR, UV-Vis, high resolution mass spectrum, and X-ray single-crystal structure analysis. It crystallizes in monoclinic system, space group P21/c with a = 9.7420(2), b = 10.4967(2), c = 14.3896(3) ?, β = 104.755(2)°, V = 1422.94(5), Z = 4, M_r = 296.32, D_c = 1.383 g/cm~3, F(000) = 616, μ = 0.690 mm~(–1), GOOF = 1.035, the final R = 0.0370 and w R = 0.1010 for 2649 observed reflections with I 2σ(I). Compound 1 in tolune exhibits deep blue luminescence with maximum emission peaks at 403 and 419 nm, lifetimes of 3.8 ns and quantum yields of ф = 0.46 at room temperature. The experimental and computational results show that the emission of the compound originates from the acridinone moiety and has π-π* character.     

Syntheses,Crystal Structures and Antibacterial Evaluation of Two New Pleuromutilin Derivatives

Two new pleuromutilin derivatives, 14-O-[(4-amino-6-methoxyl-pyrimidine-2-yl)-thioacetyl] mutilin(4) and 14-O-[4-amino-1-methyl-6-oxo-1,6-dihydropyrimidin-2-yl)thioacetyl] mutilin(5), were synthesized and structurally characterized by IR, NMR spectra, HRMS and single-crystal X-ray diffraction. These compounds contain a 5-6-8 tricyclic carbon skeleton and a pyrimidine ring. Compound 4 is in the monoclinic system, space group P1211 with a = 10.2517(4), b = 12.5655(4), c = 10.3435(4) ?, V = 1315.69(8) ?~3, Z = 2, Dc = 1.309 g/cm3, F(000) = 558, μ = 0.166 mm~(-1), S = 1.047, R = 0.0457 and w R = 0.0934 for 4721 unique reflections(R_(int) = 0.0322) with I 2σ(I). Compound 5 belongs to the orthorhombic system, space group P2_12_12_1 with a = 7.3667(4), b = 13.9990(7), c = 29.0434(13) ?, V = 2995.1(2) ?~3, Z = 4, D_c = 1.250 g/cm~3, F(000) = 1216, μ = 0.153 mm~(-1), S = 1.031, R = 0.0545 and wR = 0.0982 for 5242 unique reflections(R_(int) = 0.0476) with I 2σ(I)). The in vitro antibacterial activity study showed the title compounds 4 and 5 displayed slightly less activity against methicillin-resistant Staphylococcus aureus(MRSA) and methicillin-resistant Staphylococcus epidermidis(MRSE), and lower potent against Escherichia coli(E.coli) and Bacillus subtilis(B.subtilis) when compared to those of tiamulin fumarate.     

Two 3D Metal-organic Frameworks with 4-Fold [2+2]-type Interpenetrated hms Nets Based on a Flexible Tricarboxylic Acid

Two 3D 4-fold interpenetrated metal-organic frameworks, [Mn(L)(bpy)]_n (1) and [Cu(HL)(bpy)]_n (2)(H_3L = 4,4',4'-(benzene-1,3,5-triyl-tri(methyleneoxy)) tribenzoic acid, bpy = 4,4′-bipyridine), were synthesized under hydrothermal conditions, and characterized by element analyses, IR spectra, thermogravimetric analyses, X-ray powder diffraction and magnetic property studies. The single-crystal X-ray analyses revealed that 1 and 2 are homogeneous. 1 crystallizes in monoclinic, space group Cc with a = 26.794(2), b = 11.6346(10), c = 21.4614(18) ?, β = 91.570(2)°, V = 6687.9(10) ?~3, Z = 8, M_r = 736.59, D = 1.463 g?cm~(-3), μ = 0.458 mm~(-1)c, R_(int) = 0.0524, F(000) = 3040, the final R = 0.0844 and wR = 0.2266 for 8092 observed reflections(I 2σ(I)). 2 crystallizes in monoclinic, space group Cc with a = 27.609(12), b = 11.126(10), c = 21.490(9) ?, β = 92.131(2)°, V = 6597(5) ?~3, Z = 8, M_r = 746.21, D_c = 1503 g·cm~(-3), μ = 0.726 mm~(-1), R_(int) = 0.0542, F(000) = 3080, the final R =0.0681 and wR = 0.1831 for 6777 observed reflections(I 2σ(I)). Two compounds are 3D [2+2]-type 4-fold interpenetrated frameworks with(6~3)(6~9.8) hms topology. The magnetic study of compound 2 shows the presence of weak antiferromagnetic interaction between the Cu~Ⅱ ions in 2.     

Synthesis,Crystal Structure and Catalytic Activity of a Hexa-μ-chloro-tetrakis-(1-triphenylmethyltriazole)-μ4-oxo-tetracopper(Ⅱ)

A new Cu(Ⅱ) complex,[Cu_4Cl_6O(1-TrTz)_4]where 1-Tr Tz is 1-trityl-1H-[1,2,4]triazole,was synthesized by the reaction of 1-trityl-1H-[1,2,4]triazole with two hydrated cupric chlorides,and its structure was characterized by X-ray single-crystal diffraction.[Cu_4Cl_6O(1-TrTz)_4]is of monoclinic system,space group P21/c,a=12.5024(13),b=26.400(3),c=28.588(3)?,β=112.807(4)°,V=8698.1(16)?~3,Z=4,ρ_(calc)=1.411 g/cm~3,μ=1.265 mm~(–1),F(000)=3772,the final R=0.1293 and w R=0.3644 for 55774 observed reflections (I2s(I)),R(all data)=0.1972,w R(all data)=0.3989,completeness to theta of 25.242 is 99.9%and GOF=1.103.In the structure of[Cu_4Cl_6O(1-TrTz)_4],the central O atom is tetrahedral and is coordinated with four Cu atoms.The distance between copper and oxygen bond is 1.909(6)?.In addition,the catalytic property of this complex was investigated and it could effectively catalyze the Ullmann coupling reaction of various (hetero)aryl chlorides with azoles.     

Construction of a New(4,8)-Connected Coordination Polymer Based on the Zinc Cluster: Structure,Topology, and Luminescence

The title complex, [Zn_3(L)_2(H_2 O)_2]_n(1, H_3 L = 5-((3-formylphenoxy)methyl)isophthalic acid), has been synthesized under hydrothermal conditions and structurally characterized by single-crystal X-ray diffraction, IR spectroscopy and thermogravimetric analysis. Compound 1 exhibits a 3D binodal(4,8)-connected net based on trinuclear [Zn_3(COO)4] clusters with the topology symbol of(4~(16)·6~(12))(4~4·6~2)_2. It crystallizes in monoclinic system, space group P2_1/c, with a = 13.548(3), b = 13.291(3), c = 8.2750(1) ?, β = 97.08(3)°, V = 1478.7(6) ?~3, Z = 2, M_r = 858.6 g/mol, D_c = 1.928 mg/m~3, μ = 2.49 mm-1, F(000) = 864, GOOF = 1.12, the final R = 0.0457 and wR = 0.1329 for 4334 observed reflections with I 2σ(I). Additionally, the photoluminescent behaviours of 1 and H3 L have also been investigated in the solid state at room temperature.     

Two Three-dimensional Supramolecular Polymer Built from Mixed N-Donor and Carboxylate Ligands

Two new complexes, [Mn(L)(mmbda)(H_2O)](1) and [Co(L)(btc)(H_2O)]·H_2O(2), were synthesized by reacting the corresponding metal(Ⅱ) salts with rigid ligand 1,4-di(1Himidazol-4-yl)benzene(L) and two different carboxylic acids of 5-methylisophthalic acid(H_2mmbda) and 1,2,4-benzenetricarboxylic acid(H_3btc), respectively. The structures of the complexes were characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and PXRD. Complex 1 crystallizes in triclinic, space group P1 with a = 6.9436(4), b = 9.7306(6), c = 15.5302(10) ?, α = 73.7430(10), β = 85.1010(10), γ = 70.0360(10)o, V = 946.75(10) ?~3, Z = 2, C_(21)H_(20)N_4O_5 Mn, M_r = 463.33, D_c = 1.618 g/cm~3, μ = 0.742-1, S = 1.002, F(000) = 474, the final R = 0.0285 and wR = 0.0600 for 4328 observed reflections(I 2σ(I)). Complex 2 crystallizes in monoclinic, space group P2_1/n with a = 12.5216(12), b = 7.3312(8), c = 22.510(2) ?, β = 93.104(2)o, V = 2063.3(4) ?~3, Z = 4, C_(21)H_(18)N_4O_8Co, M_r = 513.31, D_c = 1.646 g/cm~3, μ = 0.892~(-1) mm, S = 1.096, F(000) = 1044, the final R = 0.0673 and wR = 0.1780 for 3594 observed reflections(I 2σ(I)). Both of complexes are one-dimensional(1D) chain structures and rich hydrogen bonds extend such 1D chains to form three-dimensional(3D) supramolecular polymers.     

Two New Chlorovanadates: Ba_8Cs_5V_8O_(24)Cl_(13) with [V_8O_(24)] Ring and MgCsV_2O_6Cl with [VO_3]_∞ Chain

Two new crystals of chlorovanadates,Ba_8Cs_5V_8O_(24)Cl_(13)(1) and MgCsV_2O_6Cl(2),were grown in the molten salt media. 1 crystallizes in tetragonal,space group P4/mmm(No. 123),with a = 14.801(2),c = 12.341(3) ?,V = 2703.5(8) ?~3,Z = 2,Mr = 3015.56,F(000) = 2640,μ = 11.044 mm-1,Dc = 3.704 g/cm3,the final R = 0.0380 and wR = 0.0937 for 1654 observed reflections with I 2σ(I). 2 crystallizes in a monoclinic space group C2/c(No. 15) with a = 11.128(2),b = 10.540(2),c = 6.9892(14) ?,β = 118.38(3)°,V = 721.2(2) ?~3,Z = 4,M_r = 390.55,F(000) = 712,μ = 7.997 mm-1,D_c = 3.597 g/cm~3,the final R = 0.0537 and w R = 0.1363 for 740 observed reflections with I 2σ(I). 1 exhibits a novel 8-membered-ring [V_8O_(24)] consisting of 8 corner-shared VO_4 tetrahetra,but in 2,an infinite ladder-like [VO_3]_∞ chain is formed by VO_5 square pyramids through sharing the edges.