Two Pillared-layer Co(Ⅱ) Metalorganic Frameworks Displaying Pore Modulation by Rodlike Ligands

Two novel compounds, {[Co2(epda)2(4,4-bpy)(H2O)2]·3H2O}n1 and {[Co2(epda)2(bpe)(H2O)2]3H2O}n2(H2epda=5-ethyl-pyridine-2,3-dicarboxylic acid, 4,4’-bpy=4,4’-bipyridine and bpe=1,2-di(4-pyridyl)ethylene) were solvothermally synthesized and characterized by elemental analysis, IR spectroscopy, therm ogravimetric analysis (TGA), and singlecrystal X-ray diffraction. Complex 1 is of monoclinic system, space group P21/c with a=13.344(5), b=14.724(5), c=8.267(3), β=105.840(4)°, V=1562.5(10)3, Dc=1.480 g/cm3, Mr=375.19, Z=4, F(000)=712, μ=1.121 mm-1, the final R=0.0512 and wR=0.1260 for 2890 observed reflections with I>2σ(I). 2 belongs to the monoclinic system, space group P21/c with a=14.224(4), b=14.726(4), c=8.287(2), β=99.696(4)°, V=1711.1(9)3 , Dc=1.402g/cm3, Mr=388.21, Z=4, F(000)=740, μ=1.027 mm-1 , the final R=0.0354 and wR=0.0862 for 12237 observed reflections with I>2σ(I). Both complexes present intimately related structures featuring infinite Co-carboxylate layers of [CoⅡ(epda)(H2O)]n pillared by 4,4’-bpy (or bpe) molecule to produce the microporous frameworks, unambiguously indicating that pore dimensions of the framework are regulated by the N,N’-donor pillars.     

A Two-dimensional Metallic Oxide Constructed from Molybdenum Clusters and Zn（Ⅱ）-[3-（2-pyridyl）pyrazole] Cationic Coordination Components

A new polyoxomolybdate compound [Zn(HL)2(Mo8O26)(4,4'-Bipy)]·(4,4'-Bipy) (HL = 3-(2-pyridyl)pyrazole, 4,4'-Bipy = 4,4'-bipyridine) 1 has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction, elemental analyses, TG and IR spectroscopy. The compound crystallizes in monoclinic, space group C2/c with a = 18.060(4), b = 13.870(3), c = 19.360(4) , β = 93.50(3)°, V = 4840.5(17) 3, C36H30Mo8N10O26Zn, Mr = 1851.59, Dc = 2.541 g/cm3, μ(MoKα) = 2.589 mm·1, F(000) = 3560, Z = 4, the final R = 0.0328 and wR = 0.0870 for 4005 observed reflections (I > 2σ(I)). X-ray diffraction analyses reveal that compound 1 is constructed from Mo8O264-units linked by Zn(HL)22+ and 4,4'-Bipy. Mo8O264-is connected by Zn(HL)22+ via terminal oxygen atoms along the [010] axis forming chains, which are further linked by 4,4'-Bipy along the [001] axis forming a two-dimensional network structure.     

A Novel 3D Cu(Ⅱ) Coordination Polymer Containing Mixed Ligands: Synthesis,Crystal Structure and Properties

A novel compound, {[Cu2(nbdc)2(4,4'-bpy)2(H2O)2]·2H2O}n(H2nbdc = 4-nitrobenzene-1,2-dicarboxylic acid, 4,4'-bpy = 4,4'-bipyridine), was hydrothermally synthesized and characterized by elemental analysis, IR spectroscopy, thermogravimetric analysis(TGA), and single-crystal X-ray diffraction. The complex is of orthorhombic system, space group Pbcn with a = 32.222(7), b = 7.8503(16), c = 28.389(6), V = 7181(3)3, Dc = 1.720 g/cm3, Mr = 929.74, Z = 8, F(000) = 3792, μ = 1.273 mm-1, the final R = 0.0591 and wR = 0.1378 for 4548 observed reflections with I 2σ(I). The compound exhibits a 3D self-penetrating framework with bcu net topology, in which the(46·48)-networks are joined by the H2nbdc and 4,4'-bpy linkers.     

Synthesis,Crystal Structure and Water-induced Reversible Crystal-to-amorphous Transformation Property of [{Ni(IBG)(4,4'-bipy)(H_2O)_2}·3H_2O]_n

A novel NiII complex [{Ni(IBG)(4,4'-bipy)(H2O)2}·3H2O]n 1 (H2IBG = isophthaloylbisglycine and 4,4'-bipy = 4,4'-bipyridine) has been synthesized and characterized by singlecrystal X-ray diffraction, elemental analysis, IR spectra and thermogravimetric analysis. It crystallizes in monoclinic, space group P2/c with a = 15.5420(7), b = 22.4344(1), c = 8.3455(5), β = 101.538(3)o, V = 2670.1(7)3, Z = 4, C22H32N4NiO13, Mr = 619.23, Dc = 1.443 g/cm3, F(000) = 1296.0, μ(MoKα) = 0.750 mm-1, the final R = 0.0570 and wR = 0.1445 for 2296 observed reflections with I 2σ(I). In the structure, the NiII metal center is coordinated in an octahedral environment arranged by two water molecules, two carboxylate oxygen atoms and two nitrogen atoms from two 4,4'-bipy ligands. Thermal decomposition and powder X-ray diffraction results indicate that the transformation from the crystal form, [{Ni(IBG)(4,4'-bipy)(H2O)2}·3H2O]n, to the amorphous powder, Ni(IBG)(4,4'-bipy)(H2O)2, is reversible, so the latter form may be utilized as an absorbing agent for water and water vapor.     

Supramolecular Terbium-SIP Complex Pillared by 4,4'-Bipyridyl,{[Tb(SIP)(H_2O)_5]_2(bpy)_3(H_2O)}n:Synthesis,Crystal Structure and Photoluminescence

The supramolecular terbium complex, {[Tb(SIP)(H2O)5]2(bpy)3(H2O)}n (NaH2SIP= 5-sulfoisophthalic acid monosodium salt and bpy=4,4'-bipyridyl), has been synthesized by the hydrothermal reaction of Tb4O7 with NaH2SIP and bpy at 165 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, powder X-ray diffraction and photoluminescence spectrum. It crystallizes in a monoclinic system, space group C2/c, with a= 30.6840(1), b=10.9206(2), c=17.4967(3), β=111.931(1)o, V=5438.65(14)3, Z=4, C46H52N6O25S2Tb2, Mr=1470.90, Dc=1.796 g/cm3, μ=2.747 mm-1, F(000)=2928, the final R= 0.0654 and wR=0.1322 for 3806 observed reflections with I > 2σ(I). In the neutral [Tb(SIP)(H2O)5]2 motif, the Tb(III) ions are linked by the SIP ligands to form a one-dimensional zigzag chain propagating along the c axis. The zigzag chains are linked together by hydrogen bonds and π-π stacking interactions to form a two-dimensional supramolecular framework. The uncoordinated bpy molecules act as pillars to extend the two-dimensional sheets into a distinctive pillared three-dimensional supramolecular structure through O-H···N hydrogen bonds. The photoluminescence of the complex was investigated at room temperature in the solid state.     

A New 4-Connected Ni~Ⅱ Coordination Polymer with a Novel 3D 2-Fold Interpenetrated Framework

A coordination polymer [Ni(pbc)2(H2O)]n(Hpbc = 3-pyrid-4-ylbenzoic acid) has been prepared by hydrothermal synthesis and characterized by single-crystal X-ray diffraction,IR and elemental analysis.The crystal is of monoclinic,space group C2/c with a=19.624(5),b=12.029(5),c=19.452(5),β=104.45(5)°,C24H18NiN2O5,Mr=473.11,V=4447(2)3,Dc=1.413 g/cm3,F(000)=1952,μ = 0.91 cm-1,Z = 8,the final R=0.0424 and wR=0.0871 for 3757 reflections with I2σ(I).X-ray diffraction analysis reveals that the pbc-ligands act as diconnectors to link two Ni(Ⅱ) centers and adopt two coordination modes of μ2-N,O and μ2-N,O,O to form infinite wavy nickel-carboxylate chains along the bc plane.The topological analysis of compound [Ni(pbc)2(H2O)]n reveals that it is a typical CdS framework.     

Synthesis,Characterization and Crystal Structure of an Inorganic-organic Composite Metatungstate:[Co(4,4′-bipy)_2(H_2O)_4](4,4′-H_2bipy)_2[H_2W_(12)O_(40)]·5.5H_2O

A novel hybrid compound [Co(4,4'-bipy)2(H2O)4](4,4'-H2bipy)2[H2W12O40]·5.5H2O has been synthesized from an acidified aqueous solution and characterized by elemental and thermal analyses,IR and UV spectroscopy,and single-crystal X-ray structure determination. Structure analysis indicates that the title compound is of monoclinic,space group C2/c,with a=21.315(9),b=15.303 (7),c=24.139(10),β=105.170(5)o,V=7599(6)3,Mr=3706.99,Z=4,F(000)=6616,Dc=3.231,μ=18.395 mm-1,R=0.0652 and wR=0.1594. X-ray crystallographic study shows that the title compound consists of one [Co(4,4'-bipy)2(H2O)4]2+ cation,two diprotonated 4,4'-bipyridine molecules,5.5 water molecules of crystallization,and one metatungstate polyoxoanion [H2W12O40]6-,which approaches an effective Td point symmetry. TG-DTA analysis indicates that the framework of the metatungstate polyoxoanion is collapsed at 587.0 ℃.     

A Novel Three-dimensional Ni Coordination Polymer Based on Flexible Di-carboxylate Ligand and 4,4-Pyridine： Synthesis, Characterization and Topological Analysis

A novel Ni(II) coordination polymer [Ni(dtba)(4,4′-bpy)] (1, H2dtba = 2,2′-dithio- bisbenzoic acid, 4,4′-bpy = 4,4′-bipyridine) has been synthesized by H2dtba and Ni(CH3COO)2·4H2O with exo-bidentate rigid ligand 4,4′-bpy by using hydrothermal method, and its structure was determined by single-crystal X-ray diffraction. X-ray crystal structure analysis reveals that complex 1 crystallizes in monoclinic, space group Cc with a = 11.7624(9), b = 18.7933(19), c = 10.3071(11), β = 97.6510(10)°, V = 2258.2(4)3, Z = 4, C24H16N2NiO4S2, Mr = 519.22, Dc = 1.527 g/cm3, μ = 1.079 mm-1 and F(000) = 1064. The structure was solved by direct methods and refined to R = 0.0434 and wR = 0.1000 for 3281 observed reflections (I > 2σ(I)). The coordination environment of Ni(II) is a distorted octahedron, and a three-dimensional structure was formed with the coordination effect of dtba2- and 4,4′-bpy ligands. The topological analysis reveals that the whole framework of 1 is a 2-nodal net of (52.6)(53.64.72.8) topology. The thermal stability and XRD pattern of 1 were also investigated.     

Synthesis,Crystal Structure and Properties of a Novel Nickel Citrate Ni（H_2cit）（phen）（H_2O）·3H_2O（H_4cit = Citrate Acid,phen=1,10-Phenanthroline）

A new nickel citrate compound Ni(H2cit)(phen)(H2O).3H2O(H4cit = citrate acid,phen = 1,10-phenanthroline) has been synthesized and characterized by single-crystal X-ray diffraction.It crystallizes in the trigonal system,space group P31 with a = 13.8319(13),c = 10.425(2),V = 1727.3(4)3,Dc = 1.445 g/cm3,Mr = 501.09,F(000) = 780,μ = 0.901 mm-1,Z = 3,R = 0.0760 and wR = 0.1730 for 3859 observed reflections(I > 2σ(I)).In this compound,Ni2+ cation is chelated by a phen molecule,one H2cit2-anion and one H2O molecule.The citric acid coordinates to the Ni2+ center through three functional groups:α-hydroxyl,α-carboxylate and β-carboxylate while another α-carboxylate forms hydrogen bond with surrounding H2O molecule.And the citric acid is doubly protonated.The temperature-dependent magnetic susceptibility data revealed that the compound is a paramagnetic material.     

Synthesis and Crystal Structure of a Two-dimensional Cobalt Complex with 5-Tert-butyl Isophthalic Acid

The self-assembly of Co(OAc)·4H2O with H2tbip and bipy (H2tbip = 5-tert-butyl isophthalic acid, bipy = 4,4'-bipyridine) generates one new complex, [Co3(tbip)2(Htbip)2(bipy)]n, which has been characterized by elemental analysis, X-ray diffraction, and IR spectroscopy. Single-crystal X-ray analysis reveals that it crystallizes in the triclinic space group P1 with a = 9.471(6), b = 12.597(8), c = 12.899(8), α = 84.660(7), β = 70.548(7), γ = 81.965(7)o, V = 1435.1(15)3, Mr = 1215.85, Dc = 1.407 g/cm3, Z = 1, F(000) = 629, μ(MoKα) = 0.926 mm-1, the final R = 0.0623 and wR = 0.1724. The complex consists of a tbip bridged trinuclear cobalt() unit and is further linked by 4,4'-bipyridine molecule to form a 2D supramolecular network.     

Synthesis,Crystal Structure,and Topology Analysis of One Novel Interpenetrated 2D Cobalt Coordination Polymer, {[Co(HTCB)(4,4'-btb)]·H_2O}_n

One novel cobalt coordination polymer, {[Co(HTCB)(4,4'-btb)]·H2O}n(1, H3TCB= 1,3,5-tris(4-carboxyphenyl)benzene, 4,4'-btb = 4,4'-bis(1,2,4-triazol-3-yl)biphenyl), has been synthesized and characterized by elemental analysis, IR, powder X-ray diffraction(PXRD), and thermogravimetric(TG) analyses. X-ray diffraction analysis reveals that complex 1 is a 2D 2-fold interpenetrated {44,62}-sql [Co(HTCB)(4,4'-btb)] sheet based on the 1D [Co(HTCB)]n chains and1 D [Co(4,4'-btb)]n chains. The crystal of 1 crystallizes in triclinic, space group P 1 with a =9.529(12), b = 13.914(16), c = 14.906(17), V = 1903(4) 3, Z = 2, C45H34N6CoO7, Mr = 829.71,Dc = 1.448 g/cm3, F(000) = 858 and μ(MoKα) = 0.514 mm-1. The final R = 0.0655 and wR = 0.1136 for 6603 observed reflections with I 2σ(I) and R = 0.1136 and wR = 0.1747 for all data.     

Two-dimensional Lanthanide Coordination Polymers Constructed from Ce3＋/pr3＋ Cation, Imidazole-4,5- dicarboxylate and in situ Generated Oxalate Anions

Two new lanthanide coordination polymers [Ln(C 5 H 2 N 2 O 4)(H 2 O) 2 (C 2 O 4) 0.5 ] n nH 2 O (Ln=Ce III (1) or Pr III (2);C 5 H 2 N 2 O 4=imidazole-4,5-dicarboxylate anion;C 2 O 4=oxalate anion) have been synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analyses and IR spectrum.Both compounds crystallize in monoclinic,space group P2 1 /c with a=7.5225(3),b=17.2416(6),c=8.6089(3),β=110.9610(10)°,V=1042.68(7)3,Z=4,C 6 H 8 N 2 O 9 Ce,M r=392.26,D c=2.499 g/cm 3,μ(MoKα)=4.414 mm 1,F(000)=752,the final R=0.0167 and wR=0.0412 for 1;a=7.4973(3),b=17.2113(8),c=8.5729(4),β=110.9440(10)°,V=1033.14(8)3,Z=4,C 6 H 8 N 2 O 9 Pr,M r=393.05,D c=2.527 g/cm 3,μ(MoKα)=4.764 mm 1,F(000)=756,the final R=0.0192 and wR=0.0455 for 2.X-ray diffraction analyses reveal that the lanthanide cations in compound 1 or 2 are linked by imidazole-4,5-dicarboxylate and in situ generated oxalate anions via Ln-O and Ln-N covalent bonds to form two-dimensional layered networks.The successful synthesis of compound 1 or 2 also indicates a crystallographic confirmation for the decomposition of curcumin to form oxalate anion under solvothermal conditions.     

A New 3D Layered-pillared Cobalt（II）-organic Framework Constructed by Imidazole-4,5-dicarboxylic Acid （H_3IDC） and 4,4＇-Bipyridine （bipy）

A new 3D metal-organic framework of {[Co3(IDC)2(bipy)2(py)2]·7H2O}n (1) was obtained by the hydrothermal reaction of Co(NO3)2·6H2O, imidazole-4,5-dicarboxylic acid (H3IDC), 4,4'-bipyridine (bipy), and pyridine (py), and structurally characterized by elemental analysis, infrared spectroscopy, thermal gravimetric analysis, and single-crystal X-ray diffraction. X-ray diffraction crystal structural analysis reveals that it crystallizes in orthorhombic system, space group Pccn with a = 11.1040(3), b = 19.8834(5), c = 21.3025(5), V = 4703.3(2)3, Mr = 1079.63, Z = 4, Dc = 1.525 Mg·m-3, F(000) = 2212, μ(CuKα) = 8.855 mm-1, the final R = 0.0331 and wR = 0.0713 for 2525 observed reflections with I ≥ 2σ(I). In compound 1, each cobalt(II) ion is six-coordinated with a slightly distorted octahedral coordination geometry, and each μ3-IDC3- acts as a bridge to bond three neighboring Co(II) ions, leading to an infinite 2D network layer structure of [Co3(IDC)2]n with Kagomé lattice. The adjacent layers are further linked by μ2-bipy to form an infinite 3D layered-pillared framework architecture of [Co3(IDC)2(bipy)2(py)2]n.     

Synthesis, Crystal Structure and Photoluminescent Property of a Novel Silver(I) Compound {[Ag(bpp)]_2(Hphth)(NO_3)·(H_2O)_2}_n

Self-assembly of Ag(I) nitrate, 1,3-bis(4-pyridyl)propane (bpp) and phthalic acid monopotassium salt (KHphth) in CH3OH-H2O solution produced the title complex, {[Ag(bpp)]2(Hphth)(NO3)·(H2O)2}n, which was characterized by single-crystal X-ray diffraction, elemental analysis, IR spectrum, and photoluminescent spectrum. Single-crystal X-ray analysis revealed that the complex crystallizes in a monoclinic system, space group P21/c, with a = 15.4174(5), b = 8.6398(2), c = 25.2466(8) , β = 91.072(1)o, V = 3362.34(17) 3, Z = 4, C34H37N5O9Ag2, Mr = 875.43, Dc = 1.729 g/cm3, μ = 1.228 mm-1, F(000) = 1768, the final R = 0.0749 and wR = 0.1580 for 5754 reflections with I > 2σ(I). The Ag atom is coordinated by two N atoms from two bpp molecules in an approximately linear geometry. The Ag(I) ions are linked by the bpp molecules to form one-dimensional zigzag chains propagating along the c axis. The Hphth- and nitrate counter-ions are bridged by solvent water molecules through hydrogen bonds to generate a one-dimensional chain extending along the b axis. Electrostatic interactions between cations and anions, extensive hydrogen bonds and π-π interactions are responsible for the three-dimensional supramolecular structure. In the solid state, the compound exhibits blue photoluminescence with the maximum at 436 nm upon excitation at 344 nm.     

Synthesis, Crystal Structure and Photoluminescent Property of a Novel Silver(Ⅰ) Compound {[Ag(bpp)]2(Hphth)(NO3)·(H2O)2}n

Self-assembly of Ag(Ⅰ) nitrate, 1,3-bis(4-pyridyl)propane (bpp) and phthalic acid monopotassium salt (KHphth) in CH3OH-H2O solution produced the title complex,{[Ag(bpp)]2(Hphth)(NO3)·(H2O)2}n, which was characterized by single-crystal X-ray diffraction,elemental analysis, IR spectrum, and photoluminescent spectrum. Single-crystal X-ray analysis revealed that the complex crystallizes in a monoclinic system, space group P21/c, with α =15.4174(5), b = 8.6398(2), c = 25.2466(8) (A), β = 91.072(1)°, V = 3362.34(17) (A)3, Z = 4,C34H37N5O9Ag2, Mr = 875.43, Dc = 1.729 g/cm3, μ = 1.228 mm-1, F(000) = 1768, the final R =0.0749 and wR = 0.1580 for 5754 reflections with I ＞ 2σ(I). The Ag atom is coordinated by two N atoms from two bpp molecules in an approximately linear geometry. The Ag(Ⅰ) ions are linked by the bpp molecules to form one-dimensional zigzag chains propagating along the c axis. The Hphth-and nitrate counter-ions are bridged by solvent water molecules through hydrogen bonds to generate a one-dimensional chain extending along the b axis. Electrostatic interactions between cations and anions, extensive hydrogen bonds and π-π interactions are responsible for the three-dimensional supramolecular structure. In the solid state, the compound exhibits blue photoluminescence with the maximum at 436 nm upon excitation at 344 nm.     

Hydrothermal Synthesis,Crystal Structure and Properties of a Novel Polyoxometalate {[Cu~Ⅱ(1,10-phen)]_2[PMo~Ⅵ_(11)Mo~ⅤO_(40)]} [Cu~Ⅰ(C_8N_4H_6)(C_9H_6NO)(H_2O)]

A new pseudo three-dimensional framework structure of the title compound {[CuⅡ(1,10-phen)]2[PMoⅥ11MoⅤO40]}[CuⅠ(C8N4H6)(C9H6NO)(H2O)](1) has been prepared by the hydrothermal method for the first time and characterized by elemental analyses,X-ray single-crystal diffraction and IR spectra.1 consists of two building blocks,one {[CuⅡ(1,10-phen)]2[PMoⅥ11MoⅤO40]} and one [CuⅠ(C8N4H6)(C9H6NO)(H2O)] coordinated group.Singlecrystal X-ray diffraction revealed that 1 crystallizes in the monoclinic system,space group P2/c with a=13.498(4),b=12.890(3),c=21.465(8),β=97.314o,V=3704(2)3,Mr=2693.61,Z=2,Dc=2.415 Mg/m3,μ=2.915 mm-1,F(000)=2562,S=1.009,the final R=0.0583 and wR=0.1406 for 5129 observed reflections with I2σ(I).Furthermore,compound 1 shows strong fluorescent properties in the solid state at room temperature.The electrochemical behavior of 1 has also been studied by cyclic voltammograms.     

Synthesis and Crystal Structure of Picrates of 3,5-Diamino-1,2,4-triazole

The title compound C2N5H6+C6N3O7H2-was synthesized by the reaction of 3,5-diamino-1,2,4-triazole and picric acid in the mixture of ethanol and water solution.Single crystals suitable for X-ray measurement were obtained at room temperature.The structure was characterized by elemental analysis and IR and determined by X-ray diffraction analysis.Crystallographic data:C8N8H8O7,Mr = 328.22,monoclinic,space group C2/c with a = 22.815(2),b = 4.8086(5),c = 22.564(2),β = 93.976(2)°,V = 2469.6(4)3,Dc = 1.766 g/cm3,Z = 8,μ = 0.156 mm-1,F(000) = 1344,the final R= 0.0309,wR= 0.0864.     

Synthesis, Crystal Structure and Photoluminescent Property of a Novel Silver(Ⅰ) Compound {[Ag(bpp)]2(Hphth)(NO3)·(H2O)2}n

Self-assembly of Ag(Ⅰ) nitrate, 1,3-bis(4-pyridyl)propane (bpp) and phthalic acid monopotassium salt (KHphth) in CH3OH-H2O solution produced the title complex,{[Ag(bpp)]2(Hphth)(NO3)·(H2O)2}n, which was characterized by single-crystal X-ray diffraction,elemental analysis, IR spectrum, and photoluminescent spectrum. Single-crystal X-ray analysis revealed that the complex crystallizes in a monoclinic system, space group P21/c, with α =15.4174(5), b = 8.6398(2), c = 25.2466(8) (A), β = 91.072(1)°, V = 3362.34(17) (A)3, Z = 4,C34H37N5O9Ag2, Mr = 875.43, Dc = 1.729 g/cm3, μ = 1.228 mm-1, F(000) = 1768, the final R =0.0749 and wR = 0.1580 for 5754 reflections with I ＞ 2σ(I). The Ag atom is coordinated by two N atoms from two bpp molecules in an approximately linear geometry. The Ag(Ⅰ) ions are linked by the bpp molecules to form one-dimensional zigzag chains propagating along the c axis. The Hphth-and nitrate counter-ions are bridged by solvent water molecules through hydrogen bonds to generate a one-dimensional chain extending along the b axis. Electrostatic interactions between cations and anions, extensive hydrogen bonds and π-π interactions are responsible for the three-dimensional supramolecular structure. In the solid state, the compound exhibits blue photoluminescence with the maximum at 436 nm upon excitation at 344 nm.     

A 2D Layered Thiostannate:Synthesis and Crystal Structure of [tmdpH_2]Sn_3S_7

A new thiostannate,[tmdpH2]Sn3S7 1(tmdp = 4,4'-trimethylenedipiperidine),has been synthesized under solvothermal conditions and characterized by elemental analysis,IR spectroscopy,and single-crystal X-ray diffraction analysis.In 1,the Sn3S4 secondary incomplete cubane-like building units are bridged by μ2-S atoms to form Sn12S12 rings which are then joined parallelly to the [001] plane,giving the final 2D(Sn3S72-)n layer of(6,3) network.The layers are stacked along the c axis so that 24-membered ring channels are generated,in which the organic cations are accommodated.The compound crystallizes in monoclinic,space group C2/c,with a=23.052(3),b=13.4039(12),c=18.412(2),β=120.112(4)°,V=4921.3(9)3,C13H28N2S7Sn3,Mr=792.86,Z=8,Dc=2.140 g/cm3,F(000)=3056,μ=3.619 mm-1,the final R=0.0488 and wR=0.1125 for 4607 observed reflections with I2σ(I).     

Syntheses and Crystal Structures of Two Coordination Polymers Based on a Flexible Ligand N,N＇-Diacetic Acid Imidazolium

Two coordination compounds with a flexible ligand N,N?-diacetic acid imidazolium(HDAM),{[Co(trans-DAM)(bipy)(H2O)2](OH)·4H2O}n 1 and {[Cd(trans-DAM)(bipy)(H2O)](NO3)?2H2O}n 2(bipy = 4,4'-bipyridine),were prepared and characterized by single-crystal X-ray diffraction.Compound 1 crystallizes in monoclinic,space group P2/n with a = 7.589(6),b = 11.444(2),c = 12.894(3),β = 90.99(3)°,V = 1119.8(4)3,Z = 4,C8.5H14N2O5.5Co0.5,Mr = 261.68,Dc = 1.552 g/cm3,F(000) = 546,μ = 0.832 mm-1,the final R = 0.0657 and wR = 0.1958.Compound 2 crystallizes in the monoclinic C2 space group with a = 17.479(4),b = 11.689(2),c = 11.670(2),β = 117.13(3)°,V = 2121.9(7)3,Z = 4,C17H21N5O10Cd,Mr = 567.79,Dc = 1.777 g/cm3,F(000) = 1144,μ = 1.096 mm-1,the final R = 0.0233 and wR = 0.0638.In 1,the Co(II) ions are linked by μ2-trans-DAM-and bipy ligands to build a 2D(4,4) rectangular grid layer,exhibiting a 4-connected sql net.As for 2,μ3-trans-DAM-and bipy bridge Cd(II) ions form a 2D double-layer,consisting of a couple of(4,4) grid layers,which can be viewed as a(3,4)-connected network.In both compounds,the 2D structures are stabilized by hydrogen bonding interactions to give 3D supramolecular frameworks.Additionally,FT-IR spectroscopy,UV-Visible spectroscopy,and the fluorescent properties are discussed.