Two-dimensional Supramolecular Structure of a Mercury（Ⅱ） Iodide Complex with Organosulfide

A mercury（Ⅱ） iodide complex with organosulfide [Hg（pymt）（pymtH）I] 1 （pymt = the anion of pyrimidine-2-thiolate） has been synthesized by slow evaporation of the solution at room temperature and structurally characterized by single-crystal X-ray diffraction. Basic ideas and data collected are given. X-ray diffraction analysis reveals that complex 1 is mononuclear. Crystallographic data： C8H7HgIN4S2, Mr = 550.79, monoclinic system, space group P21/c, a = 11.218（4）, b = 9.551（3）, c = 15.877（4） A^°, β = 129.697（15）°, V = 1308.9（7） A^°^3, Z = 4, Mr = 550.79, Dc = 2.795 g/cm^3, F（000） = 995, μ（MoKa） = 14.415 mm^-1, 2（MoKa） = 0.71073 A^°, T= 293（2） K, 2θmax = 54.9°, GOOF= 1.053, the final R = 0.0310 and wR = 0.0742 for 2547 observed reflections with I 〉 2σ（I） （refinement on F^2）. Complex 1 is connected through hydrogen bonds to give a one-dimensional supramolecular chain structure. Furthermore, π-π interactions are also found between the pyrimidine rings with the center-to-center distances of 3.439（4） and 3.603（4） A^°, so complex 1 expands the chains into a two-dimensional network.     

Synthesis and Crystal Structure of a Cu^2＋ Supramolecular Complex [Na2Cu（BTA）2（H2O）8]·H2O with a Three-dimensional Network Structure

A three-dimensional Cu^2＋ supramolecular complex [Na2Cu（BTA）2（H2O）8]·H2O 1 （H2BTA = bistetrazolylamine） was synthesized by reacting the aqueous solution of CuSO4·5H2O and H2BTA under stirring. The crystal structure of 1 was determined by single-crystal X-ray diffraction. The result indicates that 1 crystallizes in triclinic, space group P1, with a = 7.0518（2）, b = 12.2692（2）, c = 13.8583（3） A, α = 115.7260（10）,β = 93.2440（10）, γ = 98.3610（10）°, Mr = 573.90, V= 1059.01（4） A^3, Z = 2, De= 1.800 g·cm^-3,μ（MoKα） = 1.155 mm^-l, F（000） = 586.0, S = 1.074, the final R = 0.0273 and wR = 0.0744 for 4334 observed reflections with I 〉 2σ（I）. The Cu^2＋ ion is five-coordinated with a N4O1 donor set with r = 0.153 according to the method of Addison et al. And the Na^＋ ions form an infinite main chain through bridging O atoms from coordinated water molecules. In 1, a three-dimensional supratnolecular network is formed by O-H….O, O-H…N, N-H…O and N-H…N hydrogen bonds.     

A Novel Silver（Ⅰ）σ -Complex Supramolecular Polymer： [Ag2（o-HOPhCO2）2]n

The hydrothermal reactions of sodium o‐hydroxybenzoate with AgNO₃ yield a novel stable Ag(I) s?‐complex supramolecular polymer, [Ag₂(o‐HOPhCO₂)₂]_n. The structure of [Ag₂(o‐HOPhCO₂)₂] was solved by single crystal X‐ray diffraction analysis. It is monoclinic with space group P2Jc and unit cell parameters a=0.7394(2) nm, b= 0.8822(2) nm, c=1.0662(2) nm, β= 107.66(3)°, Z=4. The silver(I) atom is two‐coordinated by two carboxylic oxygen atoms of two o‐hydroxybenzoate ligands, and meanwhile, forms supramolecular interaction with one carbon atom of phenyl‐ring in the third o‐hydroxybenzoate group. The a‐form Ag…C supramolecular bond bridges [Ag₂(o‐HOPhCO₂)₂] units into an infinite 2D layered polymer [Ag₂(o‐HOPhCO₂)₂]_n. The coordination sphere of the silver atom is best described as a distorted T‐shaped geometry.     

A Two-dimensional Coordination Polymer of Manganese（II） and Benzimidazole-5,6-dicarboxylate

A new two-dimensional (2D) manganese(II) coordination polymer {[Mn(bidc)(H2O)2]· 2H2O}n (H2bidc = benzimidazole-5,6-dicarboxylic acid) was synthesized, and characterized by X-ray crystallography and other measurements. The complex crystallizes in the orthorhombic system, space group Pbca with a = 7.0218(7), b = 17.9701(18), c = 19.0697(19), V = 2406.3(4)3, Z = 8, Dc = 1.823 g/cm3, Mr = 330.14, F(000) = 1344, μ(MoKα) = 1.140 mm-1, S = 1.055, R = 0.0305 and wR = 0.1012 for 2130 observed reflections (I > 2σ(I)). The title complex consists of a novel 2D network with a topology of short symbol (4.82)(4.82).     

A New Two-dimensional Cd（Ⅱ） Coordination Polymer Constructed by Pyridine-2,5-dicarbohydrazide

A new two-dimensional Cd（Ⅱ） coordination polymer, [Cd（2,5-pdch）（H2O）]n·2n（ClO4）·nH2O （2,5-pdch = pyridine-2,5-dicarbohydrazide）, was prepared and characterized by elemental analysis, IR spectra and single-crystal X-ray diffraction analysis. The crystal belongs to monoclinic, space group P21/c with a = 10.905（2）, b = 11.602（1）, c = 15.034（2） A, β = 117.794 （10°, V = 1682.8（4A3, Z = 4, C7H13CdCl2NsO12, Mr = 542.52, Dc = 2.141 g/cm^3,/μ = 1.691 mm^-1, F（000） = 1072, 2（MoKa） = 0.71073A, the final R = 0.0608 and wR = 0.1329 for 2972 observed reflections with I 〉 2σ（I）. Single-crystal X-ray diffraction analysis reveals that the Cd（Ⅱ） atom displays a distorted pentagonal-bipyramidal geometry coordinated by three N atoms and three O atoms from three different 2,5-pdch ligands, and one water molecule. Interestingly, each two Cd（Ⅱ） atoms are bridged by two carbohydrazide groups of the 2,5-pdch ligands to form a dimeric unit, and such dimeric units are further connected by the 2,5-pdch ligand to generate a two-dimensional （4,4）-network.     

Synthesis,Crystal Structure and Thermal Behavior of a New 2D Barium（Ⅱ） Coordination Polymer with 1H-benzimi-dazole-5,6-dicarboxylate as the Single Ligand

The self-assembly of 1H-benzimidazole-5,6-dicarboxylic acid with barium chloride under hydrothermal conditions afforded a new 2D coordination polymer,[Ba2(L)(HL)Cl]n(1,L = 1H-benzimidazole-5,6-dicarboxylate),which was characterized by elemental analysis,infrared spectroscopy,thermogravimetric analysis,and single-crystal X-ray diffraction.Compound 1 is of monoclinic system,space group P21/c with a = 10.0145(6),b=25.6854(15),c=7.3116(4) ?,β = 99.4980(10)°,V = 1854.95(19)3,C18H9Ba2ClN4O8,Z = 4,Mr=719.42,Dc = 2.576 g/cm3,μ(MoKα) = 4.427 mm-1,F(000) = 1352,the final R = 0.0202 and wR=0.0465 for 3051 observed reflections with I > 2σ(I).It exhibits an interesting two-dimensional network structure and high thermal stability(up to 420 ℃).     

A New 2D Zinc(Ⅱ) Coordination Polymer Constructed by Imidazole-4,5-dicarboxylic Acid(H_3IDC) and 1,4-Bis(imidazol-1-ylmethyl)-benzene(bix)

A new 2D Zn(Ⅱ) coordination polymer [Zn(HIDC)(bix)0.5]n(1) was obtained by the hydrothermal reaction of ZnCl2,imidazole-4,5-dicarboxylic acid(H3IDC) and 1,4-bis(imidazol-1-ylmethyl)-benzene(bix) with a 2:2:1 mole ratio.X-ray diffraction crystal structural analysis reveals it crystallizes in monoclinic,space group P21/n with a = 12.125(3),b = 10.541(3),c = 12.484(3) ,β = 115.834(4)°,V = 1436.0(6) 3,Mr = 338.60,Z = 4,Dc = 1.566 Mg·m-3,F(000) = 684,μ(MoKα) = 1.730 mm-1,the final R = 0.0439 and wR = 0.0888 for 2101 observed reflections with I ≥ 2σ(I).In 1,each zinc(Ⅱ) ion is five-coordinated with a slightly distorted trigonal bipy-ramidal coordination geometry,and each μ2-HIDC2-acts as a bridge to bond two neighboring Zn(Ⅱ) ions,leading to a 1D zigzag chain architecture.The adjacent zigzag chains are further linked by μ2-bix to form an infinite 2D network structure.The fluorescence spectrum of 1 exhibits intense emission at 466 nm when excited at 397 nm in solid state at room temperature.     

Synthesis and Crystal Structure of a New Cadmium（Ⅱ） Supramolecular Network Containing Chelating Imidazole-4-carboxylate Ligand

A new complex, [Cd（Himc）2（H2O）2] 1, obtained from imidazole-4-carboxylatic acid （H2imc） and Cd（ClO4）2·6H2O, has been synthesized. The crystal structure was determined by X-ray diffraction. The title compound crystallizes in the orthorhombic system, space group Pccn, with a = 7.4886（11）, b = 11.9667（18）, c = 13.550（2） A, V= 1214.3（3） A3, Z = 4, Mr= 370.60, Dc = 2.027 mg/m3, F（000） = 728,μ （MoKa） = 1.829 mm^-1, the final R = 0.0243 and wR = 0.0591 for 1150 unique reflections with I 〉 2σ（I）. The cadmium（II） center in the title complex is coordinated with two oxygen and two nitrogen atoms from two bidentate chelated imidazole-4-carboxlate ligands together with two water molecules, giving a distorted octahedral coordination geometry. A one-dimensional hydrogen bonding chain is formed via intermolecular O-H...O hydrogen bonds, and such adjacent chains are further stacked through intermolecular π-π and hydrogen bonding interactions to form a 3D supramolecular framework. Complex 1 exhibits a fluorescent emission band at 290 nm （λex = 236 nm） in the solid state.     

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.     

A Novel Three-dimensional Extended Supramolecular Network Constructed from Octamolybdate Clusters and Morpholine Molecules： Nae（Hmorph）e[MosO26]·2H2O

A novel organic-inorganic hybrid, Na2(Hmorph)2[MosO26]·2H2O (1, Hmorph = morpholine), has been synthesized by convenient aqueous solution method and structurally characterized by single-crystal X-ray d...     

Crystal Structure of Dimeric Units Cd2（ncpo）2（phen）2（H2O）2 Constructed by Flexible Dicarboxylic Acid with Fluorescent Emission

A dimeric coordination complex Cd2（ncpo）2（phen）2（H2O）2 was constructed by a flexible dicarboxylic acid, 2-nitro-4-carboxylphenoxyacetic acid. Its crystal structure was determined by X-ray single-crystal diffraction analysis. The crystal is of monoclinic system, space group P21/n with a = 17.2616（3）, b = 12.7460（2）, c = 18.4041（3） A^°, β= 94.432（1）°, C42H30Cd2N6O16, Mr = 1099.52, V = 4037.09（12）A^°^3 Dc = 1.809 g/cm^3, F（000） = 2192, μ = 1.139 cm^-1 and Z = 4. The final R = 0.0218 and wR = 0.0703 for 8288 observed reflections with I 〉 2σ（I）. There are two crystallographically independent but structurally very similar molecules in the unit cell of the title complex. It is noticeable that the ligand ncpo^2- displays a good flexibility, demonstrating different modes from the rigid ligands. The luminescence property has been investigated, which shows photoluminescence at 465, 490 and 574 nm upon excitation at 320 nm in the solid state at room temperature.     

[Cd（bpy）（tp）（H2O）]n： An Interesting Brickwall-like Supramolecular Array Assembled by Intermolecular Interaction

The polymeric solid, [Cu（bpy）（tp）（H2O）]n 1 （tp = terephthalate, bpy = 2,2＇-bipyridine）, has been obtained from the hydrothermal approach and characterized by X-ray diffraction, elemental analysis, IR spectra and thermogravimetric analysis. Compound 1 crystallizes in triclinic, space group P1 with a = 9.360（2）, b = 9.872（2）, c = 10.774（2）A, α = 106.281（5）, β = 112.471（5）, γ = 96.697（3）°, V = 854.5（3）A^3, Z = 2, GOF = 1.09, R = 0.0318 and wR = 0.0845. X-ray single-crystal analysis reveals that 1 is an interesting 3D staggered brickwall-like supramolecular array assembled through aromatic π-π stacking and hydrogen bonding interactions of 1D infinite zigzag polymeric chains.     

Crystal Structure of a Two-dimensional Coordination Polymer [Ba2（phen）4（tp）2]n

A novel two-dimensional coordination polymer [Ba2(phen)4(tp)2]n(phen=1,10-phenanthroline,tp=terephthalic acid) has been synthesized with tp as bridge ligands and structurally determined by X-ray crystallography.The crystal belongs to the monoclinic system,space group C2/c,with a=18.877(4),b=18.489(4),c=15.658(3),β=103.61(3)o,V=5311.5(19)3,C32H20O4N4Ba,Mr=661.86,Z=8,F(000)=2624,μ=1.542mm-1,Dc=1.655 g/cm3,the final R= 0.0228 and wR=0.0554 for 6063 observed reflections(I2σ(I)).The structural analysis shows that each tp ligand bridges barium atoms to form a two-dimensional infinite layer.There are aromatic π-π stacking interactions between neighboring layers,and aromatic π-π interactions further extend such layers into a three-dimensional supramolecular framework.     

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

A new polyoxomolybdate compound [Ag 3 (HL) 4 ](PMo 12 O 40)] 1 (HL=3-(2-pyridyl)pyrazole) has been hydrothermally synthesized and structurally characterized by single-crystal X-ray diffraction,elemental analyses,TG and IR spectroscopy.The compound crystallizes in triclinic,space group P1 with a=10.375(3),b=12.076(3),c=13.196(4),α=84.170(4),β=71.961(3),γ=86.326(4)°,V=1563.1(7)3,C 32 H 28 Ag 3 Mo 12 N 12 O 40 P,M r=2726.52,D c=2.897 g/cm 3,μ(MoKα)=3.366 mm 1,F(000)=1284,Z=1,the final R=0.0587 and wR=0.1312 for 4139 observed reflections (I > 2σ(Ⅰ)).X-ray diffraction analyses reveal that the PMo 12 O 40 3clusters in compound 1 are linked by four Ag 3 (HL) 4 3+ units via the terminal oxygen atoms to form a two-dimensional architecture.The symmetrical unit of Ag 3 (HL) 4 3+ exhibits two distinct Ag(Ⅰ) environments:a two-coordinate {AgN 2 } site and a five-coordinate {AgN 3 O 2 } site which links to two molybdate clusters.     

Synthesis and Crystal Structure of a Novel Two-dimensional Supramolecular Complex Ni（C6H7N）2（SCN）2（H2O）2

1 INTRODUCTION Supramolecular chemistry is based on the notion of creating novel structural and functional extended systems using noncovalent interactions between prefabricated molecular or ionic building blocks[1]. More recently, the design of supramolecular architec- tures by self-assembly of small building blocks has become a major research area[2, 3] due to their poten- tial applications in many fields such as selective clathration[4, 5], molecular recognition[6, 7], catalysis[8, 9] a…     

Hydrothermal Synthesis and Crystal Structure of a Zinc（Ⅱ） Polymer with a Two-dimensional Layer Structure： [Zn（pzdc）（phen）]n·nH2O

A metal-organic coordination compound formulated as [Zn（pzdc）（phen）]n·nH2O 1 （H2pzdc = pyrazine-2,3-dicarboxylic acid, phen = 1,10-phenanthroline） has been hydrothermally synthesized and structurally characterized by elemental analysis, IR, fluorescence spectrum and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group P21/n with a = 11.607（2）, b = 11.719（2）, c = 13.140（3）A^°, β = 110.707（3）°, V= 1671.9（6）A^°3, C18H12ZnN4O5, Mr= 429.69, De = 1.707 g/cm^3,μ（MoKa） = 1.511 mm^-1, F（000） = 872, Z = 4, the final R = 0.0356 and wR = 0.0853 for 2713 observed reflections （I 〉 2σ（I））. It exhibits an interesting two-dimensional layer structure and shows yellow photoluminescent property at room temperature.     

Syntheses and Structures of Two New Cobalt Supramolecular Complexes, [Co（4,4＇-bipy）2（H2O）4]·[Co2（4,4＇-bipy）3（H2O）8]·2TST·2（4,4＇-bipy）·4H2O and [Co（4,4＇-bipy）2（H2O）4]DSNT·4,4＇-bipy

Two new cobalt（II） supramolecular complexes [Co（4,4＇-bipy）2（H2O）4]·[Co2（4,4＇-bipy）3（H2O）8]·2TST·2（4,4＇-bipy）·4H2O 1 and [Co（4,4＇-bipy）2（H2O）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 （H3TST） and 2,4-bis（p-sulfanilato）-6-diethylamino-1,3,5-triazine （H2DSNT）, 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 P21/n with a = 13.599（4）, b = 18.988（6）, c = 22.995（7） A, β = 90.273（6）°, V = 5938（3）A^3, Z = 4, C56H59Co1.5N13O17S3, Mr = 1370.74, Dc = 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 〉 2σ（I）. The crystal structure of 2 belongs to the monoclinic system, space group C2/c with a = 18.864（6）, b = 14.283（5）, c = 20.246（7）A, β = 107.799（6）°, V = 5194（3）A^3, Z = 4, C49H52CoN12O10S2, Mr = 1092.08, Dc = 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.