Syntheses and Structures of Two New Cobalt Supramolecular Complexes, [Co(4,4'-bipy)_2(H_2O)_4]· [Co_2(4,4'-bipy)3O(H_2O)_8]·2TST·2(4,4'-bipy)·4H_2 and [Co(4,4'-bipy)_2(H_2O)_4]DSNT'4,4'-bipy

Two new cobalt(Ⅱ) supramolecular complexes [Co(4,4'-bipy)_2(H_2O) _4]·[Co_2(4,4'-bipy)3-(H_2O) _8]·2TST-2(4,4'-bipy)·4H_2O 1 and [Co(4,4'-bipy) _2(H_2O) _4]DSNT·4,4'-bipy 2 based upon the assembly of Co(Ⅱ), 4,4'-bipyridine (4,4'-bipy) and two new multifunctional organic ligands, 2,4,6-tris(4-sulfophenyl-amino)-1,3,5-triazine (H_3TST) and 2,4-bis(p-sulfanilato)-6-diethylamino-1,3,5-triazine (H_2DSNT), have been prepared by hydrothermal method and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal structure of 1 is of monoclinic, space group P2_(1/n) with α= 13.599(4), b = 18.988(6), c = 22.995(7) A, β = 90.273(6)°, V= 5938(3) A~3, Z = 4, C_(56)H_(59)CO_(1.5)N_(13)O_(17)S_3, M_r = 1370.74, D_c = 1.533 g/cm~3,μ = 0.613 mm~(-1), F(000) = 2842, GOOF = 1.018, the final R = 0.0796 and wR = 0.1498 for 9019 observed reflections with I > 2o(I). The crystal structure of 2 belongs to the monoclinic system, space group C2/c with α = 18.864(6), b = 14.283(5), c = 20.246(7) A, β = 107.799(6)°, V = 5194(3) A~3, Z = 4, C_(49)H_(52)CoN_(12)O_(10)S_2, M_r = 1092.08, D_c = 1.397 g/cm~3, μ= 0.480 mm~(-1), F(000) = 2276, GOOF = 1.059, the final R = 0.0665 and wR = 0.1900 for 4887 observed reflections with I> 2σ(I). The results of X-ray crystal structure analysis revealed that complexes 1 and 2 exhibit layered supramolecular frameworks stabilized by electrostatic interactions, π-π interactions and hydrogen bonds.     

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 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 P2_12_12 with Z=4. For 1,α= 12.082(2),b = 15.447(3),c = 18.784(4)(A),V= 3505.7(12) (A)~3,M_r = 731.50,D_c = 1.386 g/cm~3,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,α=12.181(2),b=15.501(3),c=18.877(4)(A),V= 3564.3(12)(A)~3,M_r=736.33,Dc = 1.372 g/cm~3,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> 20(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,Crystal Structure and Luminescence of a Cadmium(Ⅱ) Coordination Polymer with 3,6-Connected rtl Topology

A new cadmium(Ⅱ) coordination polymer,[Cd(Hcna)_2]_n(1),was hydrothermally synthesized based on 5-(4-carboxyphenoxy)nicotinic acid(H_2cna) organic linker.X-ray singlecrystal diffraction determination reveals that 1 crystallizes in the monoclinic P2_1/c space group,with a = 10.101(2),b = 7.9139(17),c= 15.627(3) A,β= 103.364(3)°,V= 1215.4(4) A~3,Z=2,M_r= 628.81,D_c = 1.718 Mg/m~3,μ= 0.963 mm~(-1),F(000) = 628,the final R = 0.0177 and wR = 0.0432 for 2263 observed reflections with I 2σ(I).In 1,the Cd(Ⅱ) cations are connected by nicotiniate units to form a two-dimensional(2D) layer,and it is further linked through benzoate units to form a three-dimensional(3D) structure.Topologically,the structure of 1 represents a 3,6-connected 3D rtl topology.Furthermore,thermal stability and photoluminescent property of 1 have also been investigated.     

Syntheses and Crystal Structures of Two Isomeric Au Complexes

<正>Two new isomeric Au complexes,Au(PPh_3)(bmt),have been synthesized via the reaction of Au(PPh_3)Cl with 2-benzimidazolethiol(Hbmt)in dichloromethane(CH_2Cl_2)solution. Their crystal structures were determined by elemental analysis and single-crystal X-ray diffraction studies.Complex 1 crystallizes in the monoclinic system,space group C2/c with a=19.589(2),b= 21.1368(15),c=23.424(2)(?),β=108.346(4)°,V=9206.1(14)(?)~3,M_r=1216.85,D_c=1.756 g/cm~3,μ=6.566 mm~(-1),F(000)=4704,Z=8,the final R=0.0563 and wR=0.1028 for 8125 reflections with I2σ(I).Complex 2 crystallizes in the monoclinic system,space group P2_l/n with a= 9.627(3),b=21.384(8),c=22.308(8)(?),P=92.068(6)°,V=4590(3)(?)~3,M_r=1216.85,D_c=1.761 g/cm~3,μ=6.585 mm~(-1),F(000)=2352,Z=4,the final R=0.0500 and wR=0.0883 for 10477 reflections with I2σ(I).X-ray diffraction studies reveal that complexes 1 and 2 both feature a 1D chain along the a axis.     

A New Cd(Ⅱ) Coordination Compound Based on 4-(1,2,4-Triazol-4-yl)phenylacetic Acid:Synthesis,Structure and Photoluminescence Property

A new complex [Cd_2(L)_2(Cl)_2(H_2O)]_n(1) was synthesized by reacting CdCl_2·2.5 H_2O with 4-(1,2,4-triazol-4-yl)phenylacetic acid(HL) ligand.The structure of the complex was characterized by single-crystal X-ray diffraction,IR spectroscopy,elemental analysis and PXRD.Complex 1 crystallizes in triclinic,space group P21/c with a = 11.4303(8),b = 14.1792(10),c = 14.6857(10) ?,β = 96.3780(10)o,V = 2365.4(3) ?~3,Z = 4,C_(20)H_(16)Cl_2N_6O_5Cd_2,M_r = 716.09,D_c = 2.011 g/cm3,μ = 2.069 mm~(-1),S = 1.051,F(000) = 1392,the final R = 0.0458 and wR = 0.0949 for 5402 observed reflections(I 2σ(I)).Complex 1 is a two-dimensional(2D) layer structure and non-covalent bonding interactions such as C–H···π and π···π extend the 2D to form a three-dimensional supramolecular polymer.     

Mixed-ligands Self-assembly Strategy Affording a New 4-Fold Interpenetrated 3D Co(Ⅱ)-based Coordination Polymer: Synthesis,Crystal Structure and Magnetic Property

A new Co(Ⅱ)-based coordination polymer, namely [Co(L)_(0.5)(4,4?-bipy)_(0.5)(H_2 O)_2]_n(1,H_4 L = 1,3-di(3?,5?-dicarboxylphenyl)benzene, 4,4?-bipy = 4,4?-bipyridine), has been hydrothermally synthesized using the mixed-ligands self-assembly strategy and further fully characterized. The crystal structure is of monoclinic, space group C2/c with a = 18.9124(10), b = 11.6150(5), c =15.4380(6) ?, β = 110.989(5)°, V = 3166.2(2) ?~3, C_(16) H_(13) CoNO_6, M_r = 374.20, Z = 8, D_c = 1.570 g·cm–3, F(000) = 1496, μ = 1.116 mm~(–1), R = 0.0461 and wR = 0.1312 for 2328 observed reflections(I 2s(I)). The crystal structure analysis revealed that 1 is a 4-fold interpenetrated three-dimensional(3D) framework with(3,4)-connected dmd-type topology. Moreover, the thermal stability and magnetic property of 1 were also investigated.     

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 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.     

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 Theoretical Calculations of a New Co(Ⅱ) Coordination Polymer Based on 5-Nitroisophthalic Acid and Bis(imidazol) Ligands

A new complex[Co(NIPH)(mbix)]_n(1,H_2NIPH = 5-nitroisophthalic acid,mbix =l,3-bis(imidazol-l-ylmethyl)benzene) has been hydrothermally synthesized and structurally characterized by elemental analysis,IR spectrum,UV spectrum,TG and single-crystal X-ray diffraction.Pink crystals crystallize in the triclinic system,space group P1 with a = 8.3797(8),b= 10.2522(10),c= 13.4244(13) A,α=94.820(2),β=108.105(2),γ=104.816(2)°,V=1042.84(17) A~3,C_(22)H_(17)CoN_5O_6,M_r = 506.34,D_c = 1.613 g/cm~3,F(000) = 518,Z = 2,μ(MoKα) =0.876 mm~(-1),the final R = 0.0505 and wR = 0.1254 for 3267 observed reflections(I2σ(I)).The structure of 1 exhibits a two-dimensional network structure and is extended into a three-dimensional supramolecule through hydrogen bonds and n-n interactions.In addition,Natural Bond Orbital(NBO) analysis was performed by using the PBE0/LANL2 DZ method built in Gaussian 09 Program.The calculation results showed obvious covalent interactions between the coordinated atoms and Co(Ⅱ) ion.     

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.     

A Novel Zn(Ⅱ)Complex with 1D Supramolecular Water Tape Formed by Cyclic Tetrameric Water Clusters

<正>A new mixed-ligand Zn(Ⅱ)complex,[Zn(4,4'-bipy)_2(H_2O)_4]·2ANS·6H_2O(1,4,4'- bipy=4,4'-bipyridine,HANS=2-aminonaphthalene-1-sulfonic acid),has been isolated and structurally characterized by single-crystal X-ray diffraction,FT-IR spectrum,TG and elemental analysis.It crystallizes in the monoclinic system,space group P2_l/c with a=12.4852(8),b= 18.3163(12),c=10.9707(7)(?),β=114.2600(10)°,V=2287.3(3)(?)~3,D_c=1.455 g/cm~3,M_r= 1002.37,Z=2,F(000)=1048,μ=0.704 mm~(-1),the final R=0.0408 and wR=0.962 for 4029 observed reflections with I2σ(I).Interestingly,an unusual one-dimensional(1D)water tape with cyclic tetrameric water clusters can be observed in 1,which are further trapped via Zn-O coordination bonds exhibiting a 2D Zn(Ⅱ)-water layer.These 2D Zn(Ⅱ)-water layers are stacked together into a 3D interdigitated supramolecular architecture via weakπ…πinteractions,in which free ANS anions are tightly filled by hydrogen-bonding interactions.Thus,π…πand classical hydrogen-bonding interactions are found as main driving forces to stabilize the 2D Zn(Ⅱ)-water layers.     

Syntheses and Crystal Structures of Two New Compounds:[Zn(2,2'-bipy)(L)CI]_2 and [Zn(phen)(L_2)]_2(HL-3-Methylbenzoic Acid)

Compounds [Zn(2,2'-bipy)(L)CI]_2 1 and [Zn(phen)(L_2)] _2 2 (2,2'-bipy = 2,2'-bipy-ridine, HL = 3-methylbenzoic acid, phen = 1,10-phenanthroline) have been synthesized under hy-drothermal conditions. 1: monoclinic, space group C2/c, α = 20.240(4), b = 9.2960(19), c = 17.904(4) A, β = 92.63(3)°, V= 3365.1(12) A3, C_(36)H_(30)Cl_2)N_4O_4Zn_2, M_r = 784.32, Z = 4, D_c = 1.548 g/cm~3,μ = 1.631 mm~(-1), F(000) = 1600, the final R= 0.0367 and wR = 0.1289 for 3867 observed reflections (I > 2σ(I). 2: monoclinic, space group C2/c, α = 23.035(5), b = 9.0395(18), c = 23.799(5)A, β = 98.55(3)°, V= 4900.6(17) A~3, C_(56)H_(44)N_4O_8Zn_2, M_r = 1031.73, Z = 4, D_c = 1.398 g/cm~3, μ= 1.039 mm~(-1), F(000) = 2128, the final R= 0.0540 and wR = 0.1287 for 5002 observed reflections (I> 2σ(I). The two compounds have the same space group and similar isolated dinuclear structure, but different space packing structures are formed by different weak intermolecular interactions. Mo-reover, IR and luminescence spectra are also employed to study the crystal structures and pro-perties of these two compounds.     

Synthesis,Structural Characterization and Catalytic Activity of Copper(Ⅰ) Complexes with Triphenylphosphine and Pyridine Derivatives

Two new Cu(Ⅰ) complexes [CuCl(3-PyOH)(PPh_3)_2](1) and [Cu_2(μ-Cl)_2(4-Stpy)(Ph_3P)_3](2)(PyOH = hydroxypyridine; stpy = styrylpyridine) with triphenylphosphine and pyridine derivatives have been synthesized and characterized by elemental analysis and X-ray single-crystal diffraction. Compound 1 crystallizes in monoclinic, space group P2_1/c with a = 9.8945(7), b = 37.266(2), c = 10.9461(7) ?, β = 116.0750(10)°, V = 3625.3(4) ?~3, Z = 4, D_c = 1.350 Mg/cm~(-3), μ = 0.801 mm~(-1), F(000) = 1528, the final R = 0.0320 and w R = 0.0729 for 18568 observed reflections(I 2σ(I)), R(all data) = 0.0413, wR(all data) = 0.0769, completeness to theta of 25.01 is 99.9% and GOF = 1.037. Compound 2 crystallizes in monoclinic, space group P2_1/c with a = 11.290(3), b = 20.388(5), c = 24.092(6) ?, β = 102.028(4)°, V = 5424(2) ?~3, Z = 4, D_c = 1.428 Mg/cm~(-3), μ = 1.016 mm~(-1), F(000) = 2408, the final R = 0.0568 and w R = 0.1486 for 27644 observed reflections(I 2σ(I)), R(all data) = 0.0716, wR(all data) = 0.1592, completeness to theta of 25.01 is 99.9% and GOF = 1.056. Two new Cu(I) complexes have been utilized as catalysts for N-arylation of imidazole and both showed good catalytic activity.     

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.     

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.     

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.     

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.     

A Metal-organic Framework Constructed from a Rare Rod-shaped Secondary Building Unit and Its Highly Efficient Photocatalytic Activity

A new Cu(Ⅱ) coordination polymer,{[Cu_3(oba)_2(μ~3-OH)_2(H_2O)_2].6H_2O}_n(H_2 oba=4,4'-oxydibenzoic acid),was synthesized by the solvothermal route and characterized by IR,TGA and XRD.The complex crystallizes in the monoclinic system,space group P2_1/c with a=5.957(6),b=29.746(3),c=9.351(7) A,β=125.709(4)°,V=1345.4(2) A~3,Z=2,C_(28)H_(36)Cu_3O_(20),M_r=883.09,D_c=1.913 g/cm~3,F(000)=782,μ=2.427 mm~(-1),R=0.0780 and wR=0.1688 for 3120 observed reflections with I 2σ(I).The complex forms a 3D framework based on rare infinite rod-shaped secondary building units(SBUs),and C-H…π interactions play an important role in stabilizing the 3D supramolecular architecture.It shows excellent catalytic activities for the degradation of safranin O(SO) and methylene blue(MB) dyes in aqueous solution under UV light irradiation.Furthermore,the apparent rate constants have also been investigated.