Solvothermal Synthesis,Structure and the Secondorder NLO Properties of a Novel Non-metal 3-D Borophosphate:(NH_4)_2[B_2P_2O_8(OH)_2]

A new non-metal 3-D borophosphate compound formulated as(NH_4)_2[B_2P_2O_8(OH)_2](1) has been synthesized by a solvothermal method and characterized by elemental analysis, energy-dispersive X-ray spectroscopy(EDS), IR spectrum and single-crystal X-ray diffraction. The borophosphate (NH_4)_2[B_2P_2O_8(OH)_2] crystallizes in the cubic system, space group P213 with Z = 2, a = b = c = 7.586(4) ?, V = 436.6(4) ?~3, Mr = 281.64, Dc = 2.127 g/cm~3, λ = 0.71073 ?, μ = 0.551 mm-1, F(000) = 284, R = 0.0277 and w R = 0.0758 for 262 observed reflections with I 2σ(I) and S = 1.082. Its structure is constructed by the connection of PO4 and BO3(OH) tetrahedra to form a 3-D anionic framework containing 4-and 8-membered rings(MRs), with two NH_4~+ cations located in the channels of the 8-membered rings. The N–H···O hydrogen bonds are observed in its packing structure and enhanced the stability of crystal structure. In addition, its thermal stability, UV spectrum and second-order NLO properties have been also investigated.     

Synthesis and Crystal Structure of a 1-D Chain Coordination Complex {[Mn2（HCAM）3（H2bipy）]·5H2O}n

The 1-D chain coordination complex of {[Mn2（HCAM）3（H2bipy）]·5H2O}n （H3CAM = 4-hydroxypyridine-2,6-dicarboxylic acid, bipy = 4,4＇-bipyridine） has been synthesized by the reaction of 4-hydroxypyridine-2,6-dicarboxylic acid, 4,4＇-bipyridine and manganese carbonate under hydrothermal conditions, and its crystal structure was determined by X-ray diffraction method The crystal belongs to the monoclinic system, space group P21/n with a = 10.110（2）, b = 20.159（4）, c = 17.861（4）A,β = 99.67（3）°, V = 3.5884（12） nm3, Mr= 901.47, Z = 4, Dc= 1.669 g.cm^-3, μ= 0.798 mm^-1, F（000） = 1840, the final R = 0.0713 and ωR = 0.1853. The complex forms a 1-D chain bridged by HCAM, protonated 4,4-bipyridines link the 1-D chains to construct 2-D networks via N-H...O hydrogen bonds, and networks are further extended via π-π stacking and hydrogen bonds into 3-D supramolecular framework.     

Synthesis and characterization of a new open-framework zinc phosphite (4,4′-(C5H4N)2(CH2)3)·[Zn3(HPO3)4]

Employing 4,4-trimethylenedipyridine as a template,a new two-dimensional zinc phosphite (4,4-(C5H4N)2(CH2)3)· [Zn3(HPO3)4 ] has been prepared at room temperature and characterized by single-crystal X-ray diffraction,FTIR,elemental analysis,powder X-ray diffraction,and thermogravimetric analysis.The compound crystallizes in the monoclinic space group P2 1 /c,with cell parameters,a=9.3309(19),b=14.798(3),c=33.637(7),β=91.11(3),V=4643.8(16) nm 3 and Z=4.The connectivity of the ZnO4 tetrahedra and HPO 3 pseudo pyramids results in infinite corner-sharing 4-membered ring chains as second building units which are further linked by Zn O P bonds to form a 2-D layer that with interesting 8-membered ring channels along the [100] direction.The diprotonated 4,4-trimethylenedipyridine molecules sit in the middle of the layers along the [100] direction and interact with the framework via hydrogen bonds.     

An Alcohol-templated Borate Based on [B14O20（OH）6]4- Polyborate Anions

A new borate [H2EG][B7O10（OH）3] （1） based on [B14O20（OH）6]4- polyborate anions has been solvothermally synthesized in the presence of H2EG as a template （EG = ethylene glycol）. The structure was determined by single-crystal X-ray diffraction and further characterized by FFIR, elemental analysis and thermogravimetric analysis. Compound 1 crystallizes in the triclinic system, space group Pi, with a = 8.5095（4）, b = 8.8694（4）, c = 10.0756（4） A, a = 95.094（2）, β = 96.936（2）, γ = 116.844（2）°, V = 664.66（5） A3. The structure of 1 consists of [B14O20（OH）6]4- moiety, which could be regarded as the largest isolated polyborate anion so far. The anions are interlinked via hydrogen bonding to form a 3D supramolecular network, whereas the diprotonated [H2EG]2＋ are filled in the free space of inorganic borate network and interact with the inorganic framework by extensive hydrogen bonds. It is noteworthy that the EG acts not only as a solvent, but also as a template.     

Synthesis and Crystal Structure of a Novel Tetranuclear Zinc（Ⅱ） Coordination Polymer [Zn4（o-bda）4（p-pbim）4]n

A novel tetranuclear zinc（H） coordination polymer [Zn4（o-bda）a（p-pbim）4]n 1 （p-pbim = 4-pyridylbenzimidazole, o-bda2 = o-phenylenediacetic acid dianion） has been synthesized by a hydrothermal method and characterized by elemental analysis, IR and X-ray singlecrystal diffraction. The title complex crystallizes in monoclinic, space group of P21/n with α = 14.231（1）, b = 16.257（1）, c = 16.794（1） ]k, β = 100.26（1）°, V = 3823.1（2）A3, Z = 8, Dc = 1.573 g/cm^3,β = 1.321 mm^-1, F（000） = 1856, R = 0.0420 and wR = 0.111. The Zn（1） atom assumes a distorted trigonal bipyramidal geometry, involving three carboxyl O atoms from two different o-bda ligands and two N atoms from two p-pbim ligands. The Zn（2） atom is coordinated by two oxygens from two distinct bda2- anions and two nitrogen atoms from two p-pbim ligands to form a distorted tetrahedral geometry. The Zn（Ⅱ） atoms are alternately interlinked by o-bda ligands in bis-monodentate or chelating-bidentate and monodentate modes into one-dimensional undulate chains along axis c with the adjacent Zn…Zn distances of 8.32 and 8.47 A. Such neighboring chains are further extended into a 1D bi-chain structure with two different subrings A and B, which are 32- and 14-membered rings through interchain p-pbim ligands. There exists a 2D supramolecular network linked by intermolecular hydrogen-bonding interactions between the uncoordinated carboxylate 0（4） atom or coordinated carboxylate 0（7） atom and the uncoordinated imidazolyl N（2） and N（5） atoms with the O...N distances to be 2.695 and 2.807A.     

Synthesis,Crystal Structure and Biological Activity of a Novel Complex： Co（L）2（CH3OH）2Cl2 （L = 3-（1,2,4-Triazole-yl）-6-chloro-pyridazine）

The title compound, Co（L）2（CH3OH）2Cl2 （L = 3-（1,2,4-triazole-yl）-6-chloro-pyridazine） 1, has been synthesized and its crystal structure has been determined by X-ray analysis. Complex 1 crystallizes in the triclinic system, space group P1 with a = 6.018（3）, b = 9.832（5）, c = 9.921（5）A, a = 78.270（8）, β = 74.550（8）, γ = 83.807（8）°, V = 553.1（5）A^3, Z = 1, C14H16Cl4CoN10O2, Mr = 557.10, Dc = 1.673 g/cm^3, F（000） = 281,μ（MoKα） = 1.293 mm^-1, the final R = 0.0453 and wR = 0.1181 for 1539 observed reflections with I 〉 2σ（I）. The Co（II） ion is in a distorted centrosymmetric six-coordinate octahedral environment with two Ntriazole, two Omethanol and two Cl atoms. Via hydrogen bonds the configuration of 1 has been extended into 1D chains which are developed to 2D layers via π-π sticking action, and these layers are further extended into a 3D network by hydrogen bonds. The antibacterial activity of the title compound has been detected, and the results show that the ligands and cobalt（II） complex exhibit certain fungicidal activity against several bacteria. Furthermore, the spectral properties of the title compound have been also studied and discussed.     

Single-crystal Structure of ScAlMgO4

Crystals of scandium magnesium aluminate, ScAlMgO4, were grown from the melt prepared from stoichiometric quantities of Sc2O3, Al2O3 and MgO. Single-crystal X-ray diffraction indicates that ScAlMgO4 crystallizes in the space group R3 m with a = b = 3.2506（9） A, c = 25.152（8）A, V= 230.16（11）A^3, Z= 3, F（000） = 234,μ = 2.424 cm^-1, the final R = 0.0381 and wR = 0.1061 for 1874 observed reflections with I 〉 2σ（I）. In ScAlMgO4, all Sc atoms are coordinated octahedrally, whereas AI or Mg atoms are forming a tetrahedron, or in a triangular bipyramid if one distant O atom is included. The structure of ScAlMgO4 is characterized by { [AlMgO4]^3-}∞^2 layers parallel to the ab plane, and they are further connected into a 3-dimen-sional framework by Sc atoms via O（1） atoms between the layers.     

Synthesis and Crystal Structure of a New Zn(Ⅱ) Coordination Polymer Constructed by 1,2,4,5-Benzenetetracarboxylate

A new Zn(Ⅱ) coordination polymer [Zn3(btec)(OH)2(H2O)2]n (1, btec = 1,2,4,5- benzenetetracarboxylate) has been synthesized by hydrothermal reaction and its structure was determined by single-crystal X-ray diffraction analysis. The title compound crystallizes in mono- clinic, space group C2/c, with a = 19.580(3), b = 5.0137(8), c = 15.975(3), β = 121.629(2)°, V = 1335.3(4)3, C10H8O12Zn3, Mr = 516.27, Z = 4, Dc = 2.568g/cm3, μ = 5.419 mm-1, F(000) = 1016, R = 0.0590 and Rw = 0.1279 for 1110 observed reflections (I > 2σ(I)). X-ray analysis shows that the asymmetric unit of the title compound contains two crystallographically unique Zn(Ⅱ) atoms which are connected through the bridging carboxylate oxygen atoms of the btec ligands and μ2-bridging oxygen atoms of water molecules to generate an infinite one-dimensional chain. The adjacent chains are linked together through the benzene rings of the btec ligands to form a two-dimensional polymeric network. The adjacent two-dimensional layers are further connected together by the benzene rings of btec ligands to give the final three-dimensional structure. The benzene rings act as pillars between two layers.     

Crystal Structure,Thermal Behavior and Luminescence of a One-dimensional Coordination Polymer [Zn（4-CPOA）（Phen）（H2O）]n

A novel coordination polymer of [Zn（4-CPOA）（Phen）（H2O）]n （C21H16N2O6Zn,1,4-CPOA = 4-carboxylato-phenoxyacetate dianion and Phen = 1,10-phenanthroline） has been synthesized and characterized by elemental analysis,IR,TG,PL and single-crystal X-ray diffraction. The crystal crystallizes in the triclinic system,space group of P1 with a = 9.622（3）,b = 9.631（3）,c = 11.526（4）A,α = 67.719（5）,β = 71.203（5）,γ = 83.552（6）o,V = 935.5（5） A^3,Z = 2,Dc = 1.625 g/cm^3,μ = 1.357 mm^-1 and F（000） = 468. The Zn（II） ion is surrounded by three carboxylate O atoms from two different 4-CPOA groups,two N atoms from the Phen ligand and one water molecule,forming a distorted octahedral coordination configuration. The Zn（II） ions were alternately interlinked by carboxylate groups of 4-CPOA with chelating bisbidentate and monodentate modes into a one-dimensional zigzag chain having an intrachain distance of ca. 9.631（1） . Under the direction of supramolecular recognition and attraction,the adjacent chains yield a double-stranded chain through π-π stacking between the phen ligands,which was further expanded into a 2-D framework via strong C–H–π interaction （ca. 2.95（1） ） between the 4-CPOA ligands and into a 3-D supramolecular network by strong hydrogen bond between terminal water molecule and carboxyl group. TG/DTG shows that its chain skeleton is thermally stable up to 419 oC and the blue fluorescent emission of the complex was determined at 471 nm in a solid state with its long decay lifetime of 1.83 ns.     

Hydrothermal Synthesis,Crystal Structure and Thermal Stability of a Novel Water Cluster [Mn(phen)_2·H_2O·Cl]·p-FBA·3H_2O

A novel water cluster [Mn(phen)2·H2O·Cl]·p-FBA·3H2O (p-FBA = p-fluorobenzoic acid and phen = 1,10-phenanthroline) was synthesized by the hydrothermal reaction of MnCl2 with p-FBA and phen at 150 ℃ and characterized by elemental analysis,IR spectra and TG. Its crystal structure was determined by X-ray single-crystal diffraction study. The crystal belongs to the triclinic system,space group P1,with a = 10.5768(1),b = 11.5960(1),c = 12.9916(2) ,α = 101.816(2),β = 95.397(2),γ = 103.052(2)o,V = 1502.8(3) 3,Z = 2,Dc = 1.463 g/cm3,R = 0.0399 and wR = 0.0997. The crystal structure shows that the manganese(Ⅱ ) ion is six-coordinated by four nitrogen atoms,one chloride ion and one oxygen atom forming a distorted octahedral coordination geometry. The structure includes three acyclically connected water molecules and one coordinated water molecule thus forming a (H2O)4 water cluster. This water pattern forms a cross-linked discrete ring. The steady (H2O)4 is further extended into a cage-like structure by the hydrogen-bonding interaction formed by dissociative aqua molecule and Cl-ligand. The dimer structure is further extended into a one-dimensional (1D) structure through C-H···O interaction. π···π Stacking interaction among adjacent phen aromatic rings further stabilizes the crystal structure.     

Synthesis and Crystal Structure of a 1-D Chain Coordination Complex {[Mn2(HCAM)3(H2bipy)]·5H2O}n

The 1-D chain coordination complex of {[Mn2(HCAM)3(H2bipy)]·5H2O}n(H3CAM=4-hydroxypyridine-2,6-dicarboxylic acid,bipy=4,4′-bipyridine) has been synthesized by the reaction of 4-hydroxypyridine-2,6-dicarboxylic acid,4,4′-bipyridine and manganese carbonate under hydrothermal conditions,and its crystal structure was determined by X-ray diffraction method.The crystal belongs to the monoclinic system,space group P21/n with a=10.110(2),b=20.159(4),c=17.861(4) ,β=99.67(3)°,V=3.5884(12) nm3,Mr=901.47,Z=4,Dc=1.669 g·cm-3,μ=0.798 mm-1,F(000)=1840,the final R=0.0713 and wR=0.1853.The complex forms a 1-D chain bridged by HCAM,protonated 4,4-bipyridines link the 1-D chains to construct 2-D networks via N-H…O hydrogen bonds,and networks are further extended via π-π stacking and hydrogen bonds into 3-D supramolecular framework.     

Synthesis,Crystal Structure and Biological Activity of 1-（β-D-Glucopyranosyl）-3- amino-5-methyl-1H-1,2,4-triazole

The title compound 1-（β-D-glucopyranosyl）-3-amino-5-methyl- 1H- 1,2,4-triazole was synthesized and characterized by IR, 1H-NMR and elemental analysis. Its single crystals of 2H2O adduct suitable for X-ray analysis were obtained by the slow evaporation of a H2O solution and its structure was determined by single-crystal X-ray diffraction. The crystal belongs to orthorhombic, space group P212121 with a = 7.7490（15）, b = 10.424（2）, c = 17.447（4） A^°, V = 1409.3（5） A^°^3, Z= 4, C9H20N4O7, Mr = 296.29, Dc = 1.396 g/cm^3,μ = 0.120 mm^-1, S = 1.007, F（000） = 632, R = 0.0686 and wR = 0.1560 for 1217 observed reflections with I 〉 20（I）. The title molecules are linked through intermolecular hydrogen bonds to form two 1-D chain structures, and such adjacent chains are further linked by intermolecular hydrogen bonds and H2O bridges to form a 3-D supramolecular network structure. The preliminary bioassay results showed that the title compound exhibits fungicidal activities against Gibberella zeae and Colletotrichum orbiculare.     

Crystal Structures and Theoretical Calculation of Zn（Ⅱ） and Cu（Ⅱ） Supramolecular Complexes Based on Macrocyclic Triamine Ligand 1,4,7-Triazacyclodecane （tacd）

Two supramolecular complexes [Zn（tacd）2]（C6H8O4）·6H2O（1） and [Cu（tacd）2]Cl2·4H2O（2） were synthesized and characterized by elemental analysis, IR spectra, TGA and single-crystal X-ray diffraction analysis. The crystal structure showed that the metal ions in complexes 1 and 2 had similar coordination circumstance. But for the complex 2, it formed a novel two-dimensional supramolecular network with 12-membered rings and four-membered rings via hydrogen bond interaction. The thermal gravimetric analyses indicated that the two complexes had similar steps of weight-loss. On the basis of experiment, the two complexes were calculated by DFT-B3LYP/6-31G（d） in Gaussian 03. The results of calculation are in good agreement with the experiment.     

In Situ Hydrothermal Synthesis of a Mononuclear Copper（Ⅱ） Complex： Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-Hydroxyl-5-sulfoisophthalic Acid）

The mononuclear complex, Cu（H2SIP-O）（bpy）（H2O） （H4SIP-O = 4-hydroxyl- 5-sulfoisophthalic acid and bpy = 2,2＇-dipyridyl）, has been synthesized by the hydrothermal reaction of Cu（OH）2 with NaH2SIP and bpy at 160 ℃, and characterized by single-crystal X-ray diffraction, elemental analysis and IR spectrum. The new ligand 4-hydroxyl-5-sulfoisophthalic acid derived from 5-sulfoisophthalic acid ligand under an in situ hydrothermal condition. The crystal of the complex crystallizes in a triclinic system, space group P1, with a = 7.757（4）, b = 10.663（6）, c = 11.727（7）A, α = 94.272（4）, β = 104.067（7）, γ = 97.400（7）°, V= 927.4（9）A^3, Z = 2, C18H14N2O9SCu, Mr= 497.93, Dc= 1.783 g/cm^3,μ = 1.350 mm^-1, F（000） = 506, the final R = 0.0518 and wR = 0.1513 for 4180 observed reflections with I 〉 2σ（I）. The central Cu（II） ion is five-coordinated by two oxygen atoms from the H2SIP-O^2- ligand and two nitrogen atoms of bpy ligand in a distorted square-planar geometry as well as a water oxygen atom in the apical position to complete a distorted square-pyramidal coordination geometry. The mononuclear copper molecules are linked by hydrogen bonds between coordinated water molecules and sulfonate groups to form a one-dimensional double-chain structure. The chains are further held together through extensive π-π stacking interactions between the aromatic rings to form a three- dimensional supramolecular structure.     

Pi Stacking Interactions in Two TPT Derivatives and Their Photoluminescence Characters

π-π Stacking in the 2,4,6-tris（4-pyridyl）-1,3,5-triazine aromatic nitrogen-containing ligand and its metal-ligand complex Zn（TPT）2（H2O）4（OH）2 1 has been investigated by single-crystal X-ray diffraction analyses. The stacking mode of the ligand changes from the offset conformation to a perfect face-to-face alignment with the coordination to the zinc centers. The structure features are correlated with their solid-state luminescence properties. With excitation at 360 nm, free TPT ligand gives a strong fluorescent emission at 455 nm and the ligand-centered emission of the metal-ligand complex occurs at the same wavelength with lower emission intensity. The distance between the aromatic rings responds to the difference of luminescence characters.     

A One-dimensional Transition Metal Complex Constructed from 24-Membered Hinge-shaped Macrocycles with Salicylic Acid and 1,3-Bis（4-pyridyl）propane

A new 1-D coordination polymer [Cd（Hsal）2（bpp）2] 1 was hydrothermally synthesi- zed by self-assembly of the corresponding metal oxide and salicylic acid （H2sal） with exo-bidentate flexible dipyridyl ligand 1,3-bis（4-pyridyl）propane （bpp）. X-ray crystal structure analysis reveals that complex 1 crystallizes in monoclinic,space group C2/c with a = 18.942（3）,b = 12.9309（19）,c = 16.504（2） A,β = 120.072（2）°,V = 3498.3（9）A^3,Z = 4,C40H38CdN4O6,Mr = 783.14,Dc = 1.487 g/cm^3,μ = 0.679 mm^-1,F（000） = 1608,R = 0.0619 and wR = 0.1435 for 3153 observed reflections （I 〉 2σ（I））. The most remarkable feature of 1 lies in the 1-D chain by repeating [Cd2（bpp）2] units which consist of a 24-membered macrocyclic ring. The 1-D motifs are further connected by C–H… O hydrogen bonds to generate a 2-D structure. In addition,thermal stability and luminescent property of compound 1 were also documented.     

Synthesis, Characterization and Structural Determination of Ferrocene Derivatives Linked with Benzo[b]pyrans ——2-Amino-7,7-dimethyl-4-ferrocenyl-5-oxo-5,6, 7,8-tetrohydro-4H-chromene-3-carbonitrile

The title compound (C22H22N2O2Fe·CH3OH) was synthesized via a one-pot proce- dure from ferrocenylaldehyde, malononitrile and 5,5-dimethyl-1,3-cyclohexanedione using room temperature ionic liquid and pyridine as the catalysts, and characterized by elemental analysis, IR and 1H NMR. The structure was determined by X-ray single-crystal diffraction. The crystal belongs to monoclinic system, space group P21/n, with a = 9.7085(15), b = 22.951(4), c = 9.987(2) A, β = 112.494(3)°, V = 2055.9(6) A3, Z = 4, Mr = 402.28, Dc = 1.403 g/cm3, μ = 0.759 mm-1, F(000) = 868, the final R = 0.0536 and wR = 0.1449 for 4202 observed reflections with I > 2σ(I). The supramolecular single-helix chain of the title compound is formed by linking the building units with the hydrogen bond between N1 and N2. The adjacent chains are connected to a 2D layer by the hydrogen bond between N1 and O1. The adjacent layers are further linked by van der waals’ force. The CH3OH molecule is trapped in the interlayer.     

Synthesis,Properties and Crystal Structure of a New Bismuth Oxalate： Na（C5NH6） [Bi（H2O）（C2O4）2]2·4H2O

A new bismuth oxalate Na（C5NH6）[Bi（H2O）（C2O4）2]2·4H2O has been obtained under hydrothermal conditions and characterized by X-ray diffraction. It crystallizes in monoclinic, space group C2/m with a = 12.020（5）, b = 11.190（8）, c = 11.067（10）A, β= 121.78（2）°, NaBi2C13NH18O22, Mr= 981.24, V = 1265.4（16） A^3, Z = 2, Dc = 2.575 g/cm^3,μ（MoKcr） = 14.005 mm^-1, F（000） = 912, R = 0.0179 and wR = 0.0394. In the structure, the Bi（III） centers are interconnected by oxalate ligands to produce honeycomb-like layers, which are further pillared by bridging ligand oxalate molecules to form a 3-D open-framework structure. Furthermore, the title compound exhibits blue luminescence with the emission peaks located at 394nm in the solid state at room temperature, and thus it could be useful in the field of photoactive materials.     

Synthesis, Crystal Structures and Characterization of Ba5LiTiNb9O30

A new niobate compound with the chemical composition of Ba5LiTiNb9O30 was synthesized by doping Li^ into the system BaO-TiO2-Nb2O5 in conventional solid state reaction method. The crystalline structure was determined by X-ray diffraction analysis (XRD). The results showed that crystal structure of Ba5LiTiNb9O30 belongs to tetragonal tungsten bronze structure with space group P4bm and its unit cell parameters: a=b=1.2512(2) nm, c=0.4008(5)nm. The microstructure of reaction products was observed by scanning electron microscopy (SEM).     

Synthesis,Crystal Structure and Quantum Chemical Study of the Ladder Organotin Compound {[（C6H5CH2）2Sn]2（O）（Cl2）}2

The title compound {[（C6H5CH2）2Sn]2（O）（Cl2）}2 has been synthesized by the reaction of bisbenzyltin dichloride with NaOH dilute solution, and its structure was determined by X-ray diffraction. The crystal belongs to monoclinic, space group C2/c, with a = 2.5081（17）, b = 1.0089（7）, c = 2.0909（14） nm, β = 94.267（8）°, V= 5.276（6） nm^3, Z = 4, De= 1.734 g/cm^3,μ（MoKa） = 21.55 cm^-1, F（000） = 2704, R = 0.0398 and Rw = 0.1024. According to structural analysis, the tin atom adopts a distorted five-coordinate trigonal bipyramidal geometry, and the ladder-like structure is shaped by one planar four-membered Sn2O2 ring together with two planar four-membered Sn2OCl rings.