Synthesis,Crystal Structure and Characterization of a New Coordination Polymer from the Self-assembly of CoCl_2 Salt and Flexible Ligand 1,3-Bis(4-pyridyl)propane

A new 1D coordination polymer [Co（bpp）3Cl2（H2O）2]n 1 （bpp = 1,3-bis（4-pyridyl）-propane） was synthesized and characterized by elemental analysis,IR spectrum and single-crystal X-ray diffraction. The crystal belongs to the orthorhombic system,space group Ibca with a = 16.569（9）,b = 17.240（10）,c = 27.087（16） ,V = 7738（8） 3,Z = 8,Dc = 1.306 g/cm3,Mr = 760.65,λ（MoKa） = 0.71073 ,μ = 0.623 mm1,F（000） = 3192,the final R = 0.0678 and wR = 0.2011. The Co（II） atom is coordinated in a slightly distorted octahedral CoN4Cl2 geometry by two Cl atoms in the axial positions,four N atoms from the two bridging bpp ligands and two pendant bpp ligands. The CoN4Cl2 octahedra are connected by the bridging bpp ligands to form a 1D neutral coordination polymer chain. The chains are linked by face-to-face π-π interactions between adjacent pendant bpp ligands to give rise to a 3D supramolecular architecture. The photoluminescent investigation indicates that the emission of 1 is attributed to ligand-centered emission. The variable-temperature magnetic susceptibility measurement shows weak antiferromagnetic behavior in the coπmplex.

A Silver Complex of 6,7-Dicyanodipyridoquinoxaline:π-Stacking Interactions and Luminescence

The reaction of 6,7-dicyanodipyridoquinoxaline （DICNQ） with AgNO3 in a 1：1 molar ratio by solution method gave a new complex [Ag（DICNQ）2]NO3 1. Single-crystal X-ray diffraction analysis reveals that the complex crystallizes in the space group Ibca of orthorhombic system with eight formula units in a cell. Crystal data for 1： a = 15.7055（17）, b = 18.411（2）, c = 20.680（2）A, V = 5979.7（11）A3, Z = 8, C32Hl2AgN13O3, Mr = 734.42, Dc = 1.632 g/cm3, μ= 0.734 mm-1, F（000） = 2928, S = 1.023 and T= 293（2） K. The final R = 0.0659 and wR = 0.1927 for 2118 observed reflections with I 〉 2σ（I）, and R = 0.0801 and wR = 0.2196 for all data. The complex builds up a packing structure by π-π stacking interactions and shows a luminescent feature.

Synthesis, Crystal Structure and Antimicrobial Activity of {[Bis(pyridine-κN)bis(3,5-dinitrosalicylato κ-O,O')Zn(Ⅱ)][bis(pyridine-κN)Zn(Ⅱ)]}

A novel {[bis（pyridine-κN）bis（3,5-dinitrosalicylato κ-O,O＇）Zn（Ⅱ）][bis（pyridine-κN）Zn（Ⅱ）]}（C_（34）H_（24）N_8O_（14）Zn_2） was synthesized by a self-assemble method at room temperature. The molecular structure was determined by single-crystal X-ray analysis. The compound crystallizes in the monoclinic system, space group P2_1/n with a = 12.2156, b = 13.5696, c = 22.5602 A, β = 90.061o, Z = 4 and V = 3739.6（3）A^3. The new 1D binuclear coordination polymer {[bis（py-κN）bis（3,5-dinitrosal κ-O,O′） Zn（Ⅱ）][bis（py-κN）Zn（Ⅱ）]} resulted from two different types of moieties. The polymer [bis（py-κN）bis（3,5-dinitrosal κ-O,O′）Zn（Ⅱ）] unit is connected with [bis（py-κN） Zn（Ⅱ）] by zigzag topology. One zinc（Ⅱ） cation has a six-fold coordination environment, in which the metal atom is connected with four oxygen atoms of two 3,5-dinitrosalicylic acids to form equatorial bonds and two nitrogen atoms of pyridine to generate the axial bonds. Other four-fold nucleus contain two Zn-O bonds from different 3,5-dinitrosalicylic acids and two bonds with the Natom of pyridine. Antimicrobial assay results indicated that the compound showed moderate activities against different bacterial and fungal strains.

Synthesis and Crystal Structure of Binuclear Silver(I) Complex with 2-nitro-(2-pyridylsulfanylmethyl)benzene

The reaction of 2-nitro-（2-pyridylsulfanylmethyl）benzene L with silver nitrate produces a centrosymmetric binuclear complex bis（2-nitro-（2-pyridylsulfanylmethyl）benzene-N,S）- bis（nitrato-O,O）-disilver（Ⅰ）, [AgLNO3]2 1. The crystal is of triclinic, space group PI, with a = 7.383 （3）, b = 8.340（3）, c = 12..003（4） A, a = 95.069（6）, β = 93.498（5）, γ = 102.734（6）°, C24H20Ag2N6- O10S2, Mr= 832.32, V = 715.6（4） ,A^3, Z = 1, Dc = 1.931 g/cm^3, F（000） = 412,μ = 1.581 mm^-1, R= 0.0351 and wR = 0.0749 Each silver atom is tetrahedrally coordinated by two O atoms from bidentate nitrate, one S atom from a ligand and one N atom from another ligand. Furthermore, Ag- Ag interactions have been observed in the complex.

Synthesis and Crystal Structure of a New Cu(Ⅱ) Dithiocarbamate Complex CuI(prdtc)(phen)

A new mononuclear Cu（Ⅱ） dithiocarbamate complex CuI（prdtc）（phen） 1 （prdtc = N-pyrrolidinyldithiocarbamate, phen = 1,10-phenanthroline） was synthesized and characterized by elemental analysis, IR spectrum, and single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 8.7110（9）, b = 14.7143（14）, c = 14.8507（15） A, β = 109.721（6）°, V = 1791.9（3） A3, Z = 4, Dc = 1.916 g/cm3, CI7H16CulN3S2, Mr = 516.89, λ（MoKa） = 0.71073A,μ = 3.178 mm^-1, F（000） = 1012, the final R = 0.0369 and wR = 0.0987. A total of 4082 unique reflections were collected, of which 2916 with I 〉 2σ（I） were observed. The Cu（Ⅱ） atom is five-coordinated in a distorted square-pyramidal geometry by one I atom in the apical position, two S atoms from a prdtc ligand and two N atoms from a phen ligand in the basal plane. There exist face-to-face aromatic π-π stacking interactions between adjacent phen ligands stabilizing the structure and making the complex assemble into a 1D structure along the a axis. It can be concluded that the difference of the dtc flexibility and reaction conditions result in the structural difference between complex 1 and CuI（dmdtc）（phen） （dmdtc = N, N-dimethyldithiocarbamate）.

Synthesis and Crystal Structure of 4-(4,6-Dimethoxylpyrimidin-2-yl)-3-thiourea Carboxylic Acid Ethyl Ester

4-（4,6-Dimethoxyl-pyrimidin-2-yl）-3-thiourea carboxylic acid ethyl ester was synthesized by the reaction of 2-amino-4,6-dimethoxyl pyrimidine, potassium thiocyanate and methyl chloroformate in ethyl acetate. Single crystals suitable for X-ray measurement were obtained by recrystallization with the solvent of dimethyl formamide at room temperature. The crystal structure was determined by X-ray diffraction analysis. Crystallographic data： C10H14N4O4S, M, = 286.31, monoclinic, space group C2/c with a = 2.5309（3）, b = 0.67682（6）, c = 1.74237（19） nm, β = 114.744（3）°, V= 2.7106（5） nm3, Dc = 1.403 g/cm3, p = 0.225 mm-1, F（000） = 1200, Z= 8, R= 0.0514 and wR= 0.1529.

One-pot Synthesis,Characterization and Crystal Structure Determination of Novel 1,4,5-Trisubstituted 1,2,3-Triazole with Two Conformational Isomers:1-Benzyl-5-((4-methoxyphenyl)ethynyl)-4-phenyl-1H-1,2,3-triazole

The title compound l-benzyl-5-（（4-methoxyphenyl）ethynyl）-4-phenyl-1H-1,2,3-triazole（C24H19N3O） was designed and synthesized using one-pot strategy and structural characterization was done by single-crystal X-ray diffraction,NMR,IR and MS.This compound was crystallized out from an ethanolic solution in triclinic system,space group P1 with a =9.9038（9）,b = 10.2928（9）,c = 18.8715（19）A°,α = 103.541（6）,β = 90.507（7）,γ = 97.157（7）°,V =1854.2（3） A°3,Z = 4,crystal size（mm） = 0.25 × 0.1 × 0.1 and R（int） = 0.068.Its asymmetric unit contains two independent molecules.The crystal structure of the title compound is stabilized by intramolecular interactions of types C-H…N and C-H…O.Additionally,X-ray analysis reveals obvious C-H…π,π-π stacking interactions between two adjacent aromatic ring planes.

Crystal Structure of the Coordination Polymer of Sodium with Hydrazone Derivant of Acetoacetanilide

One new polymer, [Na（NPHSNPAB）（CH3OH）]n, where NPHSNPAB stands for Nphenyl-2-[2-hydroxy-3-sulfo-5-nitrophenylhydrazone]butadione-1,3, has been synthesized and characterized by ^1H NMR and FTIR spectroscopy and single-crystal X-ray diffraction. For this complex： C（17）H（17）N4NaO9S, Mr = 476.39, triclinic system, space group P1, a = 8.8741（18）, b = 10.942（2）, c = 12.039（2） A, α = 65.74（3）, β = 77.49（3）, γ = 84.30（3）o, V = 1040.3（4） A3, Z = 2, Dc = 1.521 g/cm^3, λ = 0.71073 A, F（000） = 492, S = 1.106, R = 0.0614 and w R = 0.1423 for 2945 observed reflections with I 〉 2（I）. X-ray structural analysis revealed that the structure of NPHSNPAB framework was almost planar by C–H···O, N–H···O, O–H···O, and O–H···S hydrogen bonds. Moreover, sodium（I） center was bound by six O and one N atoms, forming the coordination polymer. The molecular packing diagram showed complicated hydrogen bonds and π···π stacking interaction in the polymer. The average bond distance of the two dicyclic units（3.768 A） indicated strong π···π stacking interaction. The complex displays greenyellow emission at room temperature.

Non-covalent Bonded 3D Supramolecular Architectures Based on Acid-base Adducts

Two novel acid-base adducts,[H2L1^2＋]（Hpbda）2（1,L1 = 1,4-di（lH-imidazol-4-yl）benzene,H2pbda = 1,4-benzenedicarboxylic acid） and[H2L2^2＋]（NO3）2（2,L2 = l,4-di（l-carboxymethyl-imidazol-4-yl）benzene）,have been prepared and characterized by single-crystal X-ray diffraction,IR spectroscopy and elemental analysis.Compound 1 crystallizes in monoclinic,space group P21/n with a = 5.3525（11）,b = 9.1471（19）,c = 19.314（4） ？,β = 92.342（3）°,V= 944.8（3） A°3,Z = 2,C16H16N6O（10）,Mr = 452.35,Dc = 1.590 g/cm^3,μ = 0.135 mm^-1,S = 1.058,F（000） = 468,the final R = 0.0661 and wR = 0.1887 for 2298 observed reflections（I〉 2σ（I））.Compound 2 crystallizes in monoclinic,space group P21/c with a = 9.6923（10）,b = 17.2950（17）,c = 7.1880（7） ？,β =94.801（2）°,V= 1200.7（2）A°3,Z = 2,C（28）H（22）N4O8,Mr = 542.50,Dc = 1.501 g/cm^3,μ = 0.112 mm^-1,S= 1.060,F（000） = 564,the final R = 0.0394 and wR = 0.1017 for 2768 observed reflections（I 〉2σ（I））.In the title compounds,both of L1 and L2 ligands act as weak base to accept protons to exhibit diprotonated H2L1^2＋ and H2L2^2＋ form,which can effectively employ as hydrogen bonding donors to combine anion moieties to form binary adducts respectively.In the crystal packing diagram of two polymers,there exist extensive noncovalent interactions including charge-transfer interactions,C（N）-H…π and N-H…O,C-H…O,O-H…O hydrogen bonding interactions between co-crystal moieties which consolidate the structures of supramolecular polymers,thus generating three-dimensional（3D） frameworks.

Geochemistry and petrogenesis of Rajahmundry trap basalts of Krishna-Godavari Basin,India

The Rajahmundry Trap Basalts （RTB） are erupted through fault-controlled fissures in the Krishna-Godavari Basin （K-G Basin） of Godavari Triple Junction, occurring as a unique outcrop sandwiched between Cretaceous and Tertiary sediments along the east coast of India. Detailed geochemical studies have revealed that RTB are mid-Ti （1.74-1.92） to high-Ti （2.04-2.81） basalts with a distinct quartz tholeiitic parentage. MgO （6.2-13.12 wt.%）, Mg# （29-50） and Zr （109-202 ppm） suggest that these basalts evolved by fractional crystallization during the ascent of the parent magma along deep-seated fractures. Mod- erate to high fractionation of HREE, as indicated by （Gd/Yb）N ratios （1.71-2.31） of RTB, suggest their generation through 3-5% melting of a Fe-rich mantle corresponding to the stability fields of spinel and garnet peridotite at depths of 60-100 km. Low K2O/P2O5 （0.26-1.26）, high TiO2/P2O5 （6.74-16.79）, La/Nb （0.89-1.45）, Nb/Th 〉 8 （8.35-13）, negative anomalies at Rb reflect minimum contamination by granitic continental crust. （Nb/La）PM ratios （0.66-1.1） of RTB are attributed to endogenic contamination resulted through recycling of subducted oceanic slab into the mantle. Pronounced Ba enrichment with relative depletion in Rb indicates assimilation of Infra- and Inter-trappean sediments of estuarine to shallow marine character. Geochemical compositions such as A1203/TiO2 （3.88-6.83）, medium to high TiO2 （1.74 -2.81 wt.%）, positive Nb anomalies and LREE enrichment of these RTB attest to their mantle plume origin and indicate the generation of parent magma from a plume-related enriched mantle source with EM 1 signature. Ba/Th （46-247）, Ba/La （3.96-28.51） and Th/Nb （0.08-0.13） ratios suggest that the source enrichment process was marked by recycling of subduction-processed oceanic crust and lithospheric components into the mantle. Zr/Hf （37-41） and Zr/Ba （0.51-3.24） indicate involvement of an asthenospheric mantle source. The Rajahmundry basalts show affinity towards FOZO （focal zone mantle） and PSCL （post-Archaean subcontinental lithosphere） which reflect mixing between asthenospheric and lithospheric mantle components in their source. Origin of RTB magma is attributed to plume-lithosphere interaction and the upward movement of melt is facilitated by intrabasinal deep-seated faults in the K-G Basin.

1-D Open-channeled 3-D Supramolecular Frameworks Built with 2,3-Dihydroxybutanedioic Acid (H_4dhbd) and 2,2':6',2'-Terpyridine (tpy)~i

The complex [Cu2（H2dhbd）2（tpy）2]·CH3OH·4H2O 1 （H4dhbd =2,3-dihydroxybutanedioic acid, tpy = 2,2＇：6＇,2＇＇-terpyridine） has been hydrothermally synthesized and characterized by single-crystal X-ray diffraction analysis. The crystal is of triclinic, space groups Pi with a= 8.6859（17）, b = 11.223（2）, c = 12.275（2）A, α = 112.454（3）, β= 98.435（3）, γ = 105.593（3）°, V= 1022.5（3） A^3, Z = 1, C38H42Cu2N6O18, Mr = 997.86, Dc = 1.621 g/cm^3, μ= 1.127 mm^-1, F（000） = 514, T = 293（2） K, the final R = 0.0539 and wR = 0.1394 for 3550 observed reflections with I 〉 2σ（I）. In the dinuclear unit, two Cun atoms are bridged by two H2dhbd chelate anions, forming a 14-membered ring, in which the distance of Cu…Cu atoms is 7.0526（12）A. Adjacent dinuclear units are constituted through π-π interactions and C-H…O hydrogen-bonding interactions, fashioning the final 3-D supramolecular framework with 1-D open channels. Variable-temperature magnetic susceptibility measurement indicates the presence of weak antiferromagnetic exchange interactions between Cu^II ions.

Synthesis and Characterization of a Manganese(Ⅱ) Coordination Compound with Two-dimensional Layer Structure: {[Mn_2(IP)_2(1,4-bdc)_2]·H_2O}n

A new complex {[Mn2（IP）2（1,4-bdc）2]·H2O}n（1）（IP = 1H-imidazo[4,5-f][1,10]-phenanthroline, 1,4-H2 bdc = 1,4-benzendicarboxylic acid）, have been hydrothermally synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in monoclinic, space group Cc with a = 20.326（2）, b = 24.249（2）, c = 7.621（1）A, β = 108.546（6）, V = 3561.2（7）A3, Z = 4, Dc = 1.672 g/cm^3, μ = 0.785 mm^-1, F（000） = 1824, S = 1.067, the final R = 0.0299 and wR = 0.0752. Compound 1 possesses a 2D structural motif, in which two crystallographically independent 1,4-bdc dianions adopt the alternative mode of mixed bis（bidentate） and monodentate-bidentate coordination modes to bridge neighboring Mn（II） centers. And the 2D layers are linked up by hydrogen bonding and π···π stacking interactions to form a 3D network. The title compound has good thermal stability and exhibits photoluminescent emission maximum at 518 nm.

Simulation of secondary nucleation of polymer crystallization via a model of microscopic kinetics

We present simulations of the mechanism of secondary nucleation of polymer crystallization,based on a new model accounting for the microscopic kinetics of attaching and detaching.As the key feature of the model,we introduced multibody-interaction parameters that establish correlations between the attaching and detaching rate constants and the resulting thickness and width of the crystalline lamella.Using MATLAB and Monte Carlo method,we followed the evolution of the secondary nuclei as a function of various multibody-interaction parameters.We identified three different growth progressions of the crystal：（i） Widening,（ii） thickening and（iii） simultaneously thickening and widening of lamellar crystals,controlled by the corresponding kinetic parameters.