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,Crystal Structure and Gas Adsorption of a Two-fold Interpenetrated Three-dimensional Framework {[Cd(2-NO_2-BDC)(4,4?-DPA)]·(DMF)}_n

The reaction of Cd(NO_3)_2·4H_2O with 4,4?-dipyridylacetylene(4,4?-DPA) and 2-nitroterephthalic acid(2-NO_2-H_2BDC) in DMF/H_2O mixed solvent has afforded a compound {[Cd(2-NO_2-BDC)(4,4?-DPA)]·(DMF)}_n(1). Compound 1 has been characterized by single-crystal X-ray diffraction, powder X-ray diffraction, thermogravimetry analysis, and IR spectrum. Compound 1 crystallizes in the monoclinic system, space group P21/n, with a = 12.1488(3), b = 14.6689(3), c = 13.1615(3) ?, β = 111.809(3)o, V = 2177.63(9) ?~3, Z = 4, C_(23)H_(18)N_4O_7 Cd, M_r = 574.81, D_c = 1.753 g/cm~3, μ = 8.523 mm~(-1), F(000) = 1152, the final R = 0.0411 and wR = 0.1064 for 3589 observed reflections with I 2s(I). In compound 1, the Cd(Ⅱ) ions are linked by the carboxylate groups of 2-NO_2-BDC ligands to give a two-dimensional layered structure based on the centrosymmetric dinuclear Cd_2(COO)_2 units, which are further connected by the 4,4?-DPA ligands to produce a three-dimensional framework with pcu topology. Careful examination revealed that compound 1 is a 2-fold interpenetrating framework. Furthermore, the gas adsorption properties of 1 for N_2 and CO_2 have also been investigated.     

Crystal Structure and Magnetic Properties of a Dinuclear Terbium Compound Tb_2(μ_2-anthc)_4(anthc)_2(1,10-phen)_2

A dinuclear Tb(Ⅲ) compound, Tb_2(μ_2-anthc)_4(anthc)_2(1,10-phen)_2(1, Hanthc = 9-anthracenecarboxylic acid and 1,10-phen = 1,10-phenanthroline), was synthesized under solvothermal condition and structurally characterized by single-crystal X-ray diffraction. Compound 1 crystallizes in the triclinic system, space group P1, with a = 12.5061(12), b = 13.3168(10), c = 15.0079(12) ?, α = 110.620(7), β = 102.941(7), γ = 107.036(7)o, V = 2081.8(3) ?~3, Z = 1, C_(114)H_(70)N_4O_(12)Tb_2, M_r = 2005.58, D_c = 1.600 g/cm~3, μ = 1.759 mm~(-1), F(000) = 1008, the final R = 0.0294 and w R = 0.0608 for 8900 observed reflections with I 2s(I). In compound 1, two Tb(Ⅲ) ions are linked by four carboxylate groups of the bridging anthc– ligands to give a dinuclear Tb_2(μ_2-anthc)_4 unit wherein each Tb(III) ion is further capped by a terminal anthc– ligand and a 1,10-phen ligand in a chelating fashion. Detailed direct-current and alternating-current susceptibility measurements showed no slow magnetism relaxation phenomenon was observed for 1.     

Auxiliary Ligand Oriented Cd~(Ⅱ)-flexible Dicarboxylic Acid Coordination Frameworks:Syntheses,Structures and Properties

Two different Cd~(Ⅱ) coordination frameworks [Cd(L1)(L2)]_∞(1) and [Cd(L1)-(L3)(H_2O)]_∞(2) based on a flexible dicarboxylic acid ligand were obtained by introducing two different nitrogen heterocyclic auxiliary ligands(L1 = 3,3'-[1,3-benzenebis(carbonylimino)]bi(benzoate), L2 = 1,3-bi(4-pyridyl)propane, L3 = 4,4'-bipyridine). Complex 1 crystallizes in triclinic, space group P■ with a = 8.7415(5), b = 12.2247(7), c =16.2415(10) ?, β = 95.6790(10)°, V = 1525.11(16) ?~3, D_c = 1.553 mg·m~(-3), C_(35)H_(28)CdN_4O_6, M_r = 713.02, F(000) = 724, μ(MoKα) = 0.770 mm~(–1), Z = 2, R/wR(I 2σ(I))~a = 0.0302/0.0773. However, complex 2 crystallizes in monoclinic, space group P2_(1/n) with a = 11.4986(7), b = 23.0911(14), c = 11.9943(8) ?, β = 115.9500(10)°, V = 2863.6(3) ?~3, D_c = 1.598 mg·m~(-3), C_(32)H_(24)CdN_4O_7, M_r = 688.96, F(000) = 1392, μ(MoKα) = 0.820 mm~(–1), Z = 4, R/wR(I 2σ(I))~a = 0.0283/0.0631. The structures of two complexes were characterized. Complexes 1 and 2 have different one-dimensional(1D) chain structures. In addition, we have also made a preliminary study on the properties of the two complexes.     

Hydrothermal Synthesis and Crystal Structure of a Zinc(Ⅱ)Coordination Polymer Assembled by Dpphen and H_2btec/btec

<正>A new metal-organic coordination polymer[Zn_2(dpphen)_2(H_2btec)(btec)_(0.5)]_n (dpphen=4,7-diphenyl-1,10-phenanthroline,H_4btec=1,2,4,5-benzenetetracarboxylic acid)1 was obtained via hydrothermal synthesis and characterized by elemental analysis,TG,IR spectrum and single-crystal X-ray diffraction.The complex crystallizes in the monoclinic system,space group P2_l/n with a=16.2996(14),b=14.3332(12),c=25.247(2)(?),β=103.4050(10)°,V=5737.7(9)(?)~3, C_(63)H_(37)N_4O_(12)Zn_2,M_r=1172.71,D_c=1.358 g/cm~3,μ(MoKα)=0.902 mm~(-1),F(000)= 2396,Z=4, the final R=0.0684 and wR=0.1281 for 3728 observed reflections(I2σ(I)).It exhibits a two-dimensional network structure constructed by mixed ligands of dpphen and H_2btec/btec.     

Synthesis, Crystal Structure and Photoluminescent Properties of a New Dinuclear Copper(I) Complex [Cu_2(μ_2-dppm)_2(MeCN)_2(μ_2-MeCN)](ClO_4)_2·MeCN

The title compound [Cu_2(μ_2-dppm)_2(MeCN)_2(μ_2-MeCN)](ClO_4)_2·MeCN (dppm = bis(diphenylphosphino)methane) has been prepared and characterized. It crystallizes in the monoclinic system, space group P2_1/n, with a = 11.904(6), b = 20.755(11), c = 24.744(13) (A),β = 98.226(12)°, C_(58)H_(56)Cl_2Cu_2N_4O_8P_4,M_r= 1258.93, V=6051(5) (A)~3, Z = 4,D_c= 1.382 g/cm~3,μ = 9.52 mm~(-1), F(000) = 2592, R = 0.0533 and wR = 0.1295 for 6175 observed reflections with I > 2σ(I). Each Cu(I) center is tetrahedrally coordinated by two phosphine atoms from two bridging dppm ligands, one nitrogen atom from a terminally coordinated acetonitrile molecule, and another nitrogen atom from a μ_2-acetonitrile molecule. The two Cu(I) centers are bridged by two dppm ligands as well as a unique acetonitrile molecule. The full molecule exhibits a 'chair-like' configuration. This dinuclear complex exhibits intense or middle photoluminescence at room temperature in the solid state or actonitrile solution at 486 nm.     

A Mn(Ⅱ) Coordination Polymer with the Flexible Tripodal Ligand 1,3,5-Tris-(imidazol-l-ylmethyl)benzene

A new Mn(Ⅱ) coordination polymer {[Mn(timb)_2(H_2O)_2]·(Cl)_2·(H_2O)_2}n (1, timb =1,3,5-tris-(imidazol-1-ylmethyl)benzene) has been synthesized and characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. The title compound crystallizes in the triclinic system, space group P~-1 with a = 9.0774(13), b = 9.8720(15), c = 11.4898(16) (A), α = 93.378(3), β =95.471(3), γ = 101.101(3)°, V= 1002.6(3) (A)~3, M_r = 834.67, D_c = 1.382 g/cm~3,μ(Moka) = 0.517mm~(-1), F(000) = 435, GOF = 0.986, Z = 1, the final R = 0.0506 and wR = 0.1139 for 3517 observed reflections I＞ 2σ(I). It consists of one-dimensional double stranded chains formed through bridging bidentate timb ligands, and these chains are further connected to yield a 3D supramoleeular framework by hydrogen bonding interactions and π…π stacking interactions.     

Hydrothermal Synthesis and Crystal Structure of a New Manganese(Ⅱ) Complex with 2,4-Pyridine-dicarboxylic Acid and 2,2'-Bipyridine Ligands

A new metal-organic complex [Mn_2(PDC)_2(bipy)_2(H_2O)_2] (H_2PDC=2,4-pyridinedicarboxylic acid,bipy=2,2'-bipyridine) 1 has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,TG and single-crystal X-ray diffraction. The compound crystallizes in triclinic,space group P~(-)1 with α=7.376(3),b=9.990(4),c=11.950(5)(A),α=75.217(5),β=78.052(5),γ=70.655(5)°,V=796.0(5)(A)~3,C_(34)H_(26)Mn_2N_(6O)O_(10),M_r=788.49,D_c= 1.645 g/cm~3,μ(MoKa) = 0.866 mm~(-1),F(000)=235,Z=1,the final R=0.0425 and wR=0.0700 for 1971 observed reflections (Ⅰ > 2σ(Ⅰ)). In the crystal structure,the manganese atom is six-coordinated by two carboxylate oxygen atoms from two different PDC ligands,one aqua ligand,and three nitrogen atoms from 2,2'-bipy and PDC ligands,giving a distorted octahedral geometry. It exhibits a three-dimensional supramolecular network defined by O-H…O hydrogen-bonding interactions.     

A 3D Homochiral Mn(Ⅱ) Coordination Polymer Based on the Ligand 2,2?-(Ethane-1,2-diylbis(oxy)) Dicinnamic Acid

A 3D homochiral coordination polymer [Mn(edca)]n(1) was synthesized from a flexible coupled cinnamic acid ligand, 2,2?-(ethane-1,2-diylbis(oxy)) dicinnamic acid(H_2 edca) and MnCl_2×4 H_2 O under solvothermal conditions. The complex crystallizes in orthorhombic, space group P2_12_12_1 with a = 5.5785(8), b = 13.0393(18), c = 23.133(3) ?, V = 1682.7(4) ?~3, M_r = 407.27, D_c = 1.608 Mg/cm~3, F(000) = 836, Z = 4, the final R = 0.0240 and wR = 0.0590 for 2983 observed reflections(I 2σ(I)). In 1, the edca2+ anions alternately bridge the Mn(Ⅱ) cations to form one-dimensional(1 D) infinite helical chains of [Mn(edca)]n, which are further connected by the ligands generating a three-dimensional(3D) homochiral network. The photoluminescence of 1 was also investigated in solid state at ambient temperature.     

Crystal Structure and Luminescent Properties of a 3D Cd(Ⅱ) Compound Constructed from Succinate and 3,6-Di(4-pyridyl)pyridazine

A three-dimensional(3D) coordination polymer,[Cd(SC)(DPPD)]_n(1,H_2SC = succinic acid and DPPD = 3,6-di(4-pyridyl)pyridazine),has been synthesized by the solvothermal reaction of Cd(NO_3)_2·4H_2O with H_2 SC and DPPD at 120 oC in DMF solvent. Compound 1 crystallizes in the monoclinic system,space group P2_1/c,with a = 10.7993(4),b = 11.7705(3),c = 13.5336(6) ?,V = 1678.89(11) ?~3,Z = 4,C18H14N4O_4 Cd,M_r = 462.73,D_c = 1.831 g/cm~3,μ = 1.335 mm~(-1),F(000) = 920.0,the final R = 0.0500 and wR = 0.1567 for 3714 observed reflections with I 2s(I). In compound 1,the Cd(Ⅱ) ions are linked by the SC~(2–) ligands to give a two-dimensional(2D) undulating sheet based on the centrosymmetric dinuclear Cd_2(COO)_2 units. The 2D sheets are further connected by the DPPD ligands to produce a 3D structure,which is a 6-connected(4~4·6·~(10)·8) topological network based on the dinuclear Cd_2(COO)_2 node. Compound 1 exhibits a photoluminescent emission with a maximum at 540 nm upon excitation at 460 nm.     

Structural Characterization and Proton-conductive Property of a Lanthanide Metal-organic Framework Assembled from 1,2,4,5-Benzenetetracarboxylic Acid and Piperazine

The reaction of Pr(Ⅲ) salt with 1,2,4,5-benzenetetracarboxylic acid(H_4betc) and piperazine(pip) yielded a lanthanide metal-organic framework {[Pr(betc)(H_2O)_2](H_2pip)0.5}n(1)under hydrothermal conditions. Compound 1 was characterized by single-crystal X-ray structural analysis, elemental analysis, IR, X-ray powder diffraction, and thermal gravimetric. Compound 1crystallizes in monoclinic, space group P21/n with a = 11.023(5), b = 11.109(5), c = 11.456(5) ?, β = 110.065(5)°, V = 1317.7(9) ?~3, M_r = 471.14, Z = 4, F(000) = 920, D_c = 2.375 g/cm~3, μ(Mo Kα) = 3.761 mm-1, the final R = 0.0286 and w R = 0.0821(I 2σ(I)). Compound 1 exhibits a 2D network with(4, 4) topology, and a 3D supramolecular framework formed by hydrogen-bonding interactions. The proton conductivity of compound 1 has been investigated at ~97% relative humidity and different temperature.     

A Carboxylate-bridged Co(Ⅱ) Layer Complex: Synthesis,Structure and Magnetic Property

A 2D coordination polymer, [Co(NPA)(H_2 O)_2]_n(1, H_2 NPA = 3-nitrophthalic acid), has been synthesized by solvothermal method and characterized by single-crystal X-ray diffraction analysis, FT-IR spectroscopy, elemental analysis, thermogravimetric analysis and powder X-ray diffraction. Complex 1 crystallizes in orthorhombic space group Pbca with a = 7.2261(2), b = 14.6450(5), c = 19.6671(7) ?, V = 2081.31(11) ?~3, Z = 8, C_8 H_7 CoNO_8, M_r = 304.08, D_c = 1.941 mg/m~3, μ = 1.686 mm~(-1), S = 1.054, F(000) = 1224, the final R = 0.0248 and wR = 0.0603 for 1834 observed reflections(I 2σ(I)). The crystal structural analysis demonstrates that the Co(Ⅱ) ions in 1 are linked by single and double μ_2-1,3-bridging carboxylate bridges, forming a 2D layer structure. Moreover, magnetic property of 1 was also discussed.     

Synthesis,Crystal Structure and Photoluminescent Property of a New Zn(Ⅱ) Complex Based on 3,4-Bis(2-pyridyl)-5-(4-pyridyl)-1,2,4-triazole

The coordination polymer[Zn_(1.5)(2,2?,4??-tpt)(tpa)_2]_n(2,2?,4??-tpt=3,4-bis(2-pyridyl)-5-(4-pyridyl)-1,2,4-triazole,H_2tpa=terephthalic acid)has been obtained by solution evaporation method and characterized by elemental analysis,IR,TG and single-crystal X-ray diffraction.The title compound crystallizes in the triclinic system,space group P1,with a=10.331(3),b=10.596(1),c=14.966(3)?,β=99.029(0)o,V=1448.86(6)?~3,Z=2,D_c=1.668g/cm~3,μ=1.320 mm~(-1),F(000)=740,R=0.0359 and w R=0.0841 with I2σ(I)).In this polymer,the asymmetric unit contains two crystallographically independent Zn(II)ions in different coordination environments.Zn(1)ion is five-coordinated,forming a distorted tetragonal pyramidal geometry,while the Zn(2)ion is six-coordinated to get a distorted octahedral geometry.Each Zn(II)ion is linked by 2,2?,4??-tpt and H_2tpa ligands,forming an infinite 2D structure.The existence of O(8)–H(8)···O(2)hydrogen bonding interactions leads the 2D chains to generate a 3D structure.In addition,1 shows strong photoluminescent emissions in the solid state at room temperature,so it can be used as potential optical materials.     

Hydrothermal Synthesis and Crystal Structure of a Three-dimensional Nickel(Ⅱ) Coordination Polymer: [Ni2(NIPH)2(bimb)2.5(H2O)] n·3nH2O

<正>A new metal-organic coordination polymer [Ni_2(NIPH)_2(bimb)_2.5(H_2O)]n·3nH_2O 1 (H_2NIPH = 5- nitroisophthalic acid, bimb = 1,4-bis(imidazol-1-yl)-butane) has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. The title complex crystallizes in the orthorhombic system, space group P4(1)2(1)2 with a = 17.3533(16), b = 17.3533(16), c = 30.802(6) , V = 9275(2) ~3, C_(41)H_(49)N_(12)Ni_2O_(16), M_r = 1083.34, D_c = 1.552 g/cm~3, μ(MoKα) = 0.897 mm~(-1), F(000) = 4504, Z = 8, the final R = 0.0383 and wR = 0.0952 for 7343 observed reflections (I > 2σ(I)). It exhibits a three-dimensional network structure.     

Effect of Anionic Ancillary Ligands on Terpyridine Based Coordination Polymers: Synthesis,Crystal Structure and Fluorescence Property

By using different anionic ancillary ligands, two new coordination polymers, [Cd(L)I_2]_n(1) and {[Cd(L)_2(1,4-bdc)]·H_2O}_n(2)(L = 2,4,6-tris(4-pyridyl)pyridine, 1,4-H_2bdc = benzene-1,4-dicarboxylic acid), have been synthesized under hydrothermal conditions. Compound 1 crystallizes in monoclinic, space group C2/c with a = 11.625(2), b = 13.871(3), c = 13.676(3) ?, β = 108.11(3)°, V = 2096.0(7) ?~3, D_c = 2.144 g/cm~3, C_(20)H_(14)I_2N_4Cd, M_r = 676.55, F(000) = 1264, μ(MoKα) = 3.999 mm~(–1), Z = 4, Rint = 0.0308,(Δρ)_(max) = 0.354,(Δρ)_(min) = 0.289, R = 0.0332 and wR = 0.0721 for 2401 observed reflections(I 2σ(I)). However, compound 2 crystallizes in triclinic, space group P1 with a = 10.315(2), b = 14.060(3), c = 15.090(3) ?, β = 98.40(3)o, V = 1990.0(9) ?~3, D_c = 1.527 g/cm~3, C_(48)H_(34)N_8O_5Cd, M_r = 915.23, F(000) = 932, μ(MoKα)= 0.610 mm~(–1), Z = 2, Rint = 0.0776,(Δρ)_(max) = 0.869,(Δρ)_(min) = 0.843, R = 0.0815 and wR = 0.1930 for 6999 observed reflections(I 2σ(I)). Compound 1 is a 1D chain structure, which adopts inorganic anion I- as the counterion, and 2 exists a 2D(4,4) network constructed by benzene-1,4-dicarboxylic acid.     

A Dinuclear Cd(Ⅱ) Cluster-based Coordination Polymer:Synthesis,Structure and Luminescence Property

One two-dimensional coordination polymer with a formula of {[Cd(L)(imidazole)(H_2O)](H_2O)}n(1) was obtained by the synthetic reactions in aqueous solution using a newly synthesized H_2L(H_2L = methyl-3-hydroxy-5-carboxy-2-thiophenecarboxylate) ligand.Compound1 crystallizes in monoclinic system,space group C2/c with a = 18.3176(11),b = 8.5366(9),c =8.4152(5) ?,β = 101.789(6)o,V = 2797.1(3) ?~3,D_c = 1.979 g/cm~3,C_(10)H_(12)N_2O_7SCd,Mr = 416.68 F(000) = 1648,μ = 1.745 mm~(-1),F(000) = 1648,the final R = 0.0323 and wR = 0.0604 for 2604 observed reflections with I 2s(I).Structure analyses reveal that the compound is constructed by dinuclear Cd(Ⅱ) clusters bridged by two hydroxyl oxygens of L~(2-)anions,which features a two-dimensional network with 4-connected sql topology.Furthermore,the compound exhibits high thermal stability and intense fluorescent emission,and could be explored for potentia luminescent materials.     

Synthesis and Crystal Structure of Trans-bis(acesulfamato-O)tetraaquazinc(Ⅱ)

<正>The title compound,trans-bis(acesulfamato-O)tetraaquazinc(Ⅱ)(I,C_8H_(16)N_2O_(12)S_2Zn), crystallizes in the triclinic system,space group P_1~-with a=5.1638(5),b=8.5338(9),c=9.9583(9) (?),a=74.325(8),β=81.112(7),γ=75.800(8)°,V=407.77(7)(?)~3,Z=1,F(000)=236,R_(int)=0.085, T=296 K,the final R=0.029 and wR=0.078 for 1832 observed reflections with I2σ(I).The Zn~Ⅱcentre resides on a centre of symmetry and has a distorted octahedral geometry.The basal plane is defined by two carbonyl O atoms of two monodentate trans-oriented acesulfamato ligands and two trans-aqua ligands.The axial positions in the octahedron are occupied by two trans-aqua ligands. Intermolecular O-H…O hydrogen bonds produce R_2~2(8)and R_2~2(16)rings,which lead to two-dimensional polymeric chains.     

Two Coordination Polymers Containing Linear Co(Ⅱ)-Trinuclear and Cu(Ⅱ)-Chain Assembled from 4-Fluorocinnamic Acid and N-Donor Ligand

Two new coordination polymers,named {[Co_3(pfca)_6(phen)_2]·2H_2O}_n(1) and[Cu(pfca)_2(4,4'-bpy)(H_2O)]_n(2)(Hpfca = 4-fluorocinnamic acid and 4,4-bpy = 4,4-bipyridine),were hydrothermally synthesized and characterized by elemental analysis,IR spectroscopy,thermogravimetric analysis(TGA),and single-crystal X-ray diffraction.Complex 1 crystallizes in the triclinic crystal system,space group P_1 with a = 10.939(3),b = 12.430(4),c = 13.815(4) A,α=78.436(3),β= 70.261(3),γ= 80.268(3)°,V= 1721.8(9) A~3,D_c = 1.508 g/cm~3,M_r= 1564.06,Z = 1,F(000) = 799,μ= 0.802 mm~(-1),the final R = 0.0432 and wR = 0.1015 for 13250 observed reflections with I 2σ(I).Complex 2 is of monoclinic system,space group P2\lc with a =15.4985(14),b = 15.8424(14),c = 10.9528(10) A,β= 107.1600(10)°,V= 2569.6(4) A~3,D_c = 1.468g/cm~3,M_r = 568.02,Z = 4,F(000) = 1164,μ= 0.906 mm~(-1),the final R = 0.0371 and wR = 0.0842 for 18183 observed reflections with I 2σ(I).Complex 1 features linear Co(Ⅱ)-trinuclear units,which are assembled into a final 3D supramolecular structure through π…π stacking interactions and F-H weak interactions.Complex 2 consists of 1D polymeric Cu(Ⅱ)-chains that are further cohered together by extensive H-bonds.     

Syntheses and Structures of a New Tetrazylphosphonate Ligand and the Coordination Polymer Based on Zn~(Ⅱ)

A novel tetrazylphosphonate ligand, namely ethyl 4-(2-ethyl-2H-1,2,3,4-tetrazol-5-yl) benzylphosphonate(Et-L), was designed and successfully achieved from p-cyano benzyl chloride, based on which a zinc coordination polymer(1) with a 2D layer structure has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, TGA and X-ray single-crystal diffraction. The colorless block crystals of H_2L·H_2O were also obtained under the same hydrothermal conditions, which belongs to monoclinic system, space group P2_1/c with a = 13.3141(7), b = 5.1650(3), c = 21.9839(18) ?, β = 115.307(5)°, V = 1366.69(15) ?~3, Z = 4, D_c = 1.391 mg/cm~(-3), Mr = 349.58, F(000) = 600, R = 0.0748 and wR = 0.1917 for 2392 observed reflections(I 2σ(I)). The colorless block crystals of complex 1([Zn(L)(H_2O)]_n) also belong to monoclinic system, space group P2_1/c with a = 22.7464(10), b = 6.0430(3), c = 9.7704(4) ?, β = 92.525(4)°, V = 1341.70(10) ?~3, Z = 4, D_c = 1.731 mg/cm_(-3), M_r = 349.58, F(000) = 712, R = 0.0596 and wR = 0.1688 for 2357 observed reflections(I 2σ(I)). Only the oxygen atoms of phosphonic group are coordinated with the metal zinc probably because the hydrogen atom of tetrazole has been substituted by ethyl group. Photoluminescence properties of the complex are also investigated.     

Hydrothermal Synthesis and Crystal Structure of a Cobalt(Ⅱ) Coordination Polymer: [Co(C2O4)(bix)]n (bix=1,4-Bis(imidazol-1-ylmethyl)-benzene)

<正>A new two-dimensional cobalt coordination polymer has been prepared and fully characterized by elemental analysis, IR, TG and single-crystal X-ray diffraction. The compound [Co(C_2O_4)(bix)]_n 1 crystallizes in the monoclinic system, space group C2/c, with a = 11.549(3), b = 15.700(3), c = 9.260(2), β = 102.984(3)°, V = 1636.0(6)~3, C_(16)H_(14)CoN_4O_4, M_r = 383.23, D_c = 1.556 g/cm~3, μ(MoKα) = 1.078 mm~(-1), F(000) = 780, Z = 4, the final R = 0.0455 and wR = 0.1286 for 1483 observed reflections (I > 2σ(I)). Of the compound, the Co center is octahedrally coordinated with oxalate acting as a tetra-dentate ligand coordinated to the cobalt atom and each bix serving as a bridging ligand by employing two N-donors to coordinate with the Co center. An infinite {Co_2(C_2O_4)_2}_∞ chain is formed along the a axis. Furthermore, the 1D chains are held together via bix ligands to generate a two-dimensional network structure with 1D coronal-like channels (ca. 5.691 × 15.700).