Hydrothermal Synthesis and Crystal Structure of a New Polyoxovanadate: [Mn(en)3]2en0.5[HV8VV8IVO38(Cl)]·4.5H2O (en = Ethylenediamine)

A new compound has been synthesized under hydrothermal conditions and characterized by IR, elemental analysis, XPS and single-crystal X-ray diffraction analysis. The title compound [Mn(en)3]2en0.5[HV16O38(Cl)]·4.5H2O crystallizes in monoclinic, space group C2/c, with a = 17.016(4), b = 18.858(4), c = 18.872(4) (A), β = 93.667(4)°, V = 6043(2) (A)3, Z = 4, Dc = 2.242 g/cm3, Mr = 2040.12, F(000) = 4020, μ = 2.895 mm-1, Rint = 0.0921, R = 0.0649 and wR = 0.1325. Single-crystal X-ray structure analysis indicates that the title compound consists of a polyanion [HV8VV8IVO38(Cl)]4( cage, two [Mn(en)3]22 cations, four and a half lattice waters and a half ethylenediamine. In addition, intermolecular O-H…N,O-H…O and C-H…O and C-H…O hydrogen bonds link the molecules together to form a three-dimensional structure.     

Hydrothermal Synthesis and Crystal Structure of a New Polyoxovanadate:[Mn(en)_3]_2en_(0.5)[HV_8~ⅤV_8~ⅣO_(38)(Cl)]·4.5H_2O(en=Ethylenediamine)

A new compound has been synthesized under hydrothermal conditions and characterized by IR,elemental analysis,XPS and single-crystal X-ray diffraction analysis. The title compound [Mn(en)3]2en0.5[HV16O38(Cl)]·4.5H2O crystallizes in monoclinic,space group C2/c,with a=17.016(4),b=18.858(4),c=18.872(4),β=93.667(4)o,V=6043(2)3,Z=4,Dc=2.242 g/cm3,Mr=2040.12,F(000)=4020,μ=2.895 mm-1,Rint=0.0921,R=0.0649 and wR=0.1325. Single-crystal X-ray structure analysis indicates that the title compound consists of a polyanion [HV8VV8IVO38(Cl)]4-cage,two [Mn(en)3]22+ cations,four and a half lattice waters and a half ethylenediamine. In addition,intermolecular O-H···N,O-H···O,N-H···O and C-H···O hydrogen bonds link the molecules together to form a three-dimensional structure.     

Synthesis,Structure and Electrochemical Property of a Supramolecular Compound（H2en）2[Cu（en）2（H3O）2][Mo8O28]

A supramolecular compound(H2en)2[Cu(en)2(H3O)2][Mo8O28](en=ethylenediamine) was hydrothermally prepared and confirmed by elemental analysis and TG analysis.Single-crystal X-ray analysis reveals that the crystal crystallizes in the triclinic system,space group P1 with a=9.4635(4),b=9.8645(5),c=10.9794(5),α=69.2050(10),β=72.3730(10),γ=78.4510(10)o,Mr=1559.55,V=908.24(7)3,Z=1,Dc=2.851 g/m3,F(000)=749,μ=3.350 mm-1,S=1.000,the final R=0.0217 and wR=0.0567.The compound consists of(H2en)2+,[Mo8O28]8-anion and [Cu(en)2(H3O)2]2+ cations and constructs a 3D supramolecular structure through hydrogen bonds between the nitrogen atoms from en of [Cu(en)2(H3O)2]4+ fragments and the terminal oxygen atoms from the [Mo8O28]8-polyoxoanions.The electrochemical behavior of this compound has been studied in detail based on a solid bulk modified carbon paste electrode of compound(CPE).     

Synthesis and Crystal Structure of an Ionic Compound [Fe（CN）6·（PhCHeNC9H7）4]·12H2O

A novel ionic compound [Fe（CN）6·（PhCHeNC9H7）4]·12H2O
（C70H80FeN10O12, Mr = 1309.29） has been synthesized and its structure was characterized by I-R, elemental analysis and X-ray diffraction. The compound crystaUizes in triclinic, space group P1, with a = 10.968（7）, b = 11.466（7）, c = 14.077（8）A, α= 87.014（7）, β= 78.124（7）, γ = 72.708（7）°, V = 1654.1（17）A3, Z = 1, Dc = 1.314 g·cm^-3, F（000） = 692, p = 0.298 mm^-1, the final R = 0.0519 and wR = 0.1355. The building unit of the title compound consists of four （PhCH2N＋C9H7） ions, one [Fe（CN）6]4- anion, and a dozen water molecules. According to the structural analysis, [Fe（CN）6]4- ions are linked together by O-H…O and O-H…N hydrogen bonds, while （PhCH2N＋C9HT） and [Fe（CN）6]4- ions interact with each other by electrostatic force to form an ionic compound.     

Hydrothermal Synthesis and Crystal Structure of [Cu（en）2（H2O）]2{PW11.5Cu0.5O40[Cu（en）2] }·2H2O

A transition metal substituted polyoxotungstate, [Cu（en）2（H2O）]2{PW11.5Cu0.5O40[Cu（en）2] }·2H2O
1 based on Keggin frameworks, has bccn hydrothcrmally synthesized and characterized by IR, TGA and single-crystal X-ray structural analysis. It is interesting to find that the structure unit contains two different valence cations, narncly, one [Cu（1）（en）2（H2O）]^＋ and one [Cu（2）（en）2（H2O）]^2＋. Data for the crystal： orthorhombic system, space group Pbca, a = 21.585（2）, b = 20.695（2）, c = 26.137（3）A, V = 11675（2）A^3, Z = 8, Mr = 3428.23, Dc = 3.901 g/cm^3, F（000） = 12156,μ（MoKα） = 23.932 mm^-1, the final R = 0.0468 and wR = 0.0969 for 6927 observed reflections （I 〉 2σ（I））.     

Synthesis,Crystal Structure and Antitumor Activities of Ethyl 5-methyl-4-morpholino- 2-（3-Methyl-phenylamino）-furo [2,3-d] pyrimidine-6-carboxylate

The title compound （C21H24N4O4, Mr = 396.44） has been synthesized by the func- tionalized ethyl 4-chloro-6-methyl-2-arylamino-furo[2,3-d]pyrimidine-5-carboxylates and mor- pholine. Its structure was confirmed by means of 1H NMR IR, MS and elemental analysis. The crystal structure of the title compound was determined by X-ray single-crystal diffraction. The compound crystallizes in triclinic system, space group P1, a = 7.9919（8）, b = 9.9312（1）, c = 12.9380（13） A, aα = 86.987（2）, β = 83.604（2）, γ = 89.641（2）°, V = 1019.08（18） A3, Z = 2, F（000） = 420, Dc = 1.292 g/cm3,μ = 0.091 mm-1, R = 0.0602 and wR = 0.1548 for 3943 independent （Rint = 0.0639） and 3414 observed （I 〉 2σ（I）） reflections, lntermolecular N-H…O and π-π stacking interactions contributed to the stability of the structure. The preliminary biological test indicated the title compound exhibited cytotoxicity against human lung cancer cell lines.     

Ring-opened Crystal Structure and Photochromism of 2,2-Bis（4-tertiary butyl phenyl）-3H-naphtho[2,1-b]pyran

The title compound, 2,2-bis（4-tertial butyl phenyl） naphthopyran, has been prepared and characterized by means of IR, ^1H NMR and elemental analysis, and its crystal structure was determined with X-ray diffraction in the ring-opened form after hydrolyzation. It belongs to monoclinic, space group P21/c, with a = 14.358（3）, b = 7.6725（15）, c = 24.470（5） А, β= 97.147（4）°, C_33H_36O2, Mr=464.62, V= 2674.8（9）А^3, Z = 4, Dc = 1.154 g/cm^3,μ= 0.070 mm^-1, F（000） = 1000, the final R = 0.0514 and wR = 0.1272 for 5444 observed reflections （I 〉 2σ（I））. X-ray analysis revealed that the C（13）-O（1） bond of the title compound cracks after UV irradiation, the six-membered heterocycles are destroyed, and zwitterionic intermediates come into being. The molecular structure in the ring-opened form is obtained after hydrolyzation. It is infrequent that the single-crystal structure is determined in a ring-opened form. A two-dimensional framework is formed by O-H…O and CAr-H…O hydrogen bonds. The UV-vis spectra show that the title compound exhibits excellent photochromic properties in solutions and polymers.     

The First Example of a Supramolecular Structure Containing [2-（1H-Pyrazol-3-yl）-pyridine] Complex and both α- and β-Octamolybdates

The title compound, [Ni（C8N3H7）3]4[Mo8O26]2·6H2O 1, has been synthesized from the reaction of 2-（1H-pyrazol-3-yl）-pyridine （L） with （NH4）2MoO4·2H2O and NiCl2·6H2O. Elemental analysis, IR, UV spectra and X-ray single-crystal diffraction were carried out to determine the composition and crystal structure of the compound. Crystal data： C96H96Mo16N36Ni4O58, Mr = 4451.97, monoclinic system, space group P21/n, a = 20.846（5）, b = 14.825（5）, c = 23.122（5） A ,β= 91.594（5）°, V = 7143（3）A^3, Z = 2, F（000） = 4344, Dc = 2.070 g/cm^3,μ = 1.968 mm^-1, R = 0.0452 and wR = 0.1056 for 17102 independent reflections （Rint = 0.0442） and 11074 observed reflections （I 〉 2σ（I））. Structural analysis indicates that two kinds of octamolybdates （[α-Mo8026]^4- and [β-Mo8026]^4-） co-exist in the compound. This is the first example of a supramolecular structure containing L complex as well as both α- and β-octamolybdate clusters.     

Synthesis,Crystal Structure and Theoretical Calculation of [2-（2,6-Dioxacyclohexyl）-5-methoxylphenols]2

The title compound [2-（2,6-dioxacyclohexyl）-5-methoxylphenols]2 was synthesized by the reaction of 2-hydroxyl-3-methoxylbenzaldehyde and 1,3-propanediol in the presence of DMF-DMS adduct and characterized by IR spectrum, UV-Vis spectrum and X-ray crystallography. The title compound belongs to monoclinic, space group P21 with a = 9.8967（10）, b = 8.2240（9）, c = 13.3654（14） A^°, β= 90.016（2）°, C11H14O4, Mr = 210.22, V = 1087.8（2）A^°3, Z = 4, Dc = 1.284 Mg/m^3, F（000） = 448,μ = 0.098 mm^-1, the final R = 0.0300 and wR = 0.0761 for 2070 observed reflections with I 〉 2σ（I）. The molecules are connected via intermolecular O-H…O hydrogen bonds into a 2D network structure. Moreover, theoretical investigations of the title compound with HF/6-31G（d） method were performed, and its stability, frontier molecular orbital composition and Mulliken charge distribution were also discussed. The compound is a bis-molecule. The two molecules stay together and could not be separated. Two crystallographically independent molecules exist in an asymmetric unit. The bond lengths and bond angles of the two molecules are slightly different with each other.     

Synthesis,Crystal Structure and Antitumor Activity in Vitro of a New Benzoate Binuclear Cupper（ Ⅱ） Complex

The title compound, [Cu2（C7H5O2）4（C2H6O）2], was synthesized by the reaction of benzoic acid, copper acetate and ethanol in an aqueous solution. Trypan blue dye exclusion method was used in experiment. X-ray single-crystal analysis has revealed that compound 1 （C32H32Cu2O10） crystallizes in the monoclinic system, space group C2/c, Mr = 703.66, a = 47.340（5）, b = 6.6613（4）, c = 22.028（2）A,β = 113.284（4）°, V = 6380.6（10） A^3, Z = 8, Dc= 1.465 g/cm^3, F（000） = 2896,μ = 1.388 mm^-11, the final R = 0.0515 and wR = 0.1172 for 5712 observed reflections with I 〉 2σ（I）. X-ray crystal structure analysis suggests that compound [CH2（C7H5O2）4（C2H6O）2] has a binuclear structure with two Cu（II） atoms coordinated by four benzoate groups and two ethanol molecules. The crystal packing is stabilized by intermolecular O-H...O hydrogen bonds. The compound inhibits the proliferation of K562 cells （chronic myeloid leukemic cells） significantly and dose-dependently in 48 h, and IC50 of K562 is 17.3μg/mL by trypan blue dye exclusion method.     

Synthesis,Structure and Properties of a Novel Copper（II）-2,2- biimidazole Complex-supported Compound： [Cu（H2biim）2] { [Cu（H2biim）2]2 [H10W12O44] }.8H2O

A new copper（II）-2,2＇-biimidazole metal-organic POMs-supported compound [Cu（H2biim）2]{[Cu（H2biim）212[H10W12O44]}＇8H2O （H2biim = 2,2＇-biimidazole） has been success- fully synthesized under hydrothermal conditions and characterized by single-crystal X-ray diffraction, IR spectroscopy, elemental analysis and TG. The crystal adopts space group Pi with a = 11.800（2）, b = 13.437（3）, c = 13.685（3） A, V = 1922.5（7） A3, D,. = 3.507 g/cm3, C36H62Cu3N24W12O52, M,. = 4059.92, F（000） = 1837,μ = 18.796 mm-1, Z = 1, R = 0.0579 and wR = 0.1465 for 8734 observed reflections （I 〉 2σ（I））. X-ray crystallography analysis exhibits that the title compound consists of one [H10W12044]6- polyanion and three [Cu（H2biim）2] units. And significant π-π stacking interactions and intermolecular O-H-,.O or N-H.＇-O hydrogen-bonding interactions lead to a three-dimensional supramolecular framework. Thermal stability and magnetic property of the complex have also been investigated.     

Synthesis and Crystal Structure of [2-Hydroxy- 5-（4-hydroxy-3-phenyliminomethylbenzyl）-benzylidene]-phenyl-amine

The title compound [2-hydroxy-5-（4-hydroxy-3-phenyliminomethyl-benzyl）-benzylidene]-phenyl-amine （C27H22N2O2, Mr = 406.47） was synthesized by 5,5′-methylene-bissalicylal- dehyde with aminobenezene, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group C2/c with a = 4.4026（6）, b = 1.501（13）, c = 0.95818（12） nm, β = 90.868（2）°, V= 4.2813（9） nm^3, Z= 8, Dc= 1.292 g/cm^3,μ = 0.010, F（000） = 1744, R = 0.0576 and wR = 0.1450 for 3766 observed reflections with I 〉 2σ（I）. X-ray analysis reveals that the molecule has a pair of intramolecular OH…N hydrogen bonds.     

Synthesis and Crystal Structure of （E）-ethyl 6-benzyl-2-[（cyclopropylmethylamino）（4-fluorophenylamino）-methyleneamino]-4,5,6,7-tetrahydrothieno[2,3-c]pyridine-3-carboxylate ethanol monosolvate

The crystal structure of the new title compound (E)-ethyl 6-benzyl-2-[(cyclopropylmethylamino)(4-fluorophenylamino)methyleneamino]-4,5,6,7-tetrahydrothieno[2,3-c]pyridine-3-carboxylate ethanol monosolvate (C28H31FN 4O2S·C2H6O, Mr=552.70) has been prepared and determined by single-crystal X-ray diffraction. The crystal is of monoclinic system, space group P21/c with a=13.806(10), b=10.850(7), c=19.938(14), β=98.842(9)° , V=2951(4)3 , Z=4, Dc=1.244g/cm 3 , F(000)=1176, μ=0.153 mm-1 , MoKα radiation (λ=0.71073), R=0.0758 and wR=0.2234 for 4262 observed reflections with I > 2σ(I). Intramolecular N-H…S and C-H…N interactions as well as intermolecular N-H…O and O-H…N hydrogen bonds help to stabilize the crystal structure. X-ray diffraction analysis reveals that the asymmetric unit contains one title molecule and one ethanol molecule.     

Synthesis,Crystal Structure and Characterization of a Cobalt Coordination Polymer： [Co（1,4-ndc）（L） （H2O）]n

The title coordination polymer, [Co（1,4-ndc）（L）（H2O）]n 1 （1,4-H2ndc = 1,4-na- phthalenedicarboxylic acid and L =1-（5-（1H-imidazol- 1-yl）pentyl）- 1H-imidazole） has been hydrothermally synthesized and characterized by IR and single-crystal X-ray diffraction. It crystallizes in monoclinic, space group P21/n with a = 12.4333（12）, b = 13.2963（13）, c = 13.4678（13）A, α =β = 90°, y =107.302（2）°, V= 2125.7（4）A^3, Z = 4, CoC22H22N4O5, Mr = 481.37, De = 1.504 g/cm^3, F（000） = 996, μ（MoKa） = 0.850 mm^-1, R = 0.0472 and wR = 0.0984. Compound 1 exhibits a two-dimensional layer structure. The O-H...O and C-H...O hydrogen bonds stabilize the structure of 1.     

Synthesis and Crystal Structure of Trans-4-[ （5-（ 2,4-Dichlorophenoxy）-3-methyl-1-phenyl-1H-pyrazol-4-yl）methyleneamino]-1,5-dimethyl-2-phenyl-l,2-dihydropyrazol-3-one

The title compound trans-4-[（5-（2,4-dichlorophenoxy）-3-methyl- 1-phenyl-1H-pyrazol-4-yl）methyleneamino]- 1,5-dimethyl-2-phenyl-1,2-dihydropyrazol-3-one 3 （C28H23Cl2N5O2, Mr = 532.41） has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction analysis. It crystallizes in triclinic, space group P1- with a = 8.9438（4）, b = 11.6065（5）, c = 14.2215（6）A, α = 112.566（1）, β = 92.324（2）, γ = 102.91（1）°, V= 1315.65（10） A^3, Z = 2, Dc = 1.344 g/cm^3,μ（MoKa） = 0.282 mm^-1, λ = 0.71073 A, F（000） = 552, the final R = 0.0587 and wR = 0.1578 for 5071 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that the product is a thermodynamically stable trans isomer. Intra- and intermolecular C（ 12）-H（12）…O（1） and C（28）-H（28）...O（1）# 1 hydrogen bonds were observed in the title compound.     

Synthesis,Structure and Properties of Two New Coordination Polymers Based on 4-[（8-Hydroxy-5-quinolinyl）azo]-benzenesulfonic Acid

Two new coordination polymers based on 4-[（8-hydroxy-5-quinolinyl）azo]-benzenesulfonic acid（H2L）,{[CdL（H2O）2]·H2O}n（1） and {[CdL（en）]·EtOH}n（2）（en=ethylenediamine）,were solvothermally synthesized and structurally characterized by single-crystal X-ray diffraction.Compounds 1 and 2 exhibit infinite 1D ladder-shaped chain structures,which are isostructural except that the two coordinating water molecules in compound 1 were replaced by one en molecule in compound 2 due to the use of different organic base.Compounds 1 and 2 were constructed into different supramolecular frameworks by hydrogen bonding and π…π stacking interactions.In addition,the fluorescent properties of compounds 1 and 2 were investigated.Furthermore,they were also investigated via IR spectral analysis,elemental analysis,powder X-ray diffraction（PXRD） and thermogravimetric analysis（TGA）.     

Synthesis and Crystal Structure of 5,17-Diformyl-11,23-di（tert-butyl）25,26,27,28-tetrapropoxy-calix[4]arene

The title compound 5,17-diformyl-11,23-di（tert-butyl）-25,26,27,28-tetrapropoxycalix[4]arene has been synthesized by selective formylation of 5,11,17,23-tetra（tert-butyl）25,26,27,28-tetrahydroxycalix[4]arene in three steps and characterized by1H NMR and X-ray single-crystal diffraction.The crystal belongs to the monoclinic system,space group C2/c with a = 25.760（3）,b = 10.9952（10）,c = 18.630（2）,β = 119.985（4）°,V = 4570.4（9）3,Z = 4,Dc = 1.106 g/cm3,Mr = 761.01,F（000） = 1648,μ = 0.071 mm-1,MoKa radiation（λ = 0.71073）,R = 0.0710 and wR = 0.2411 for 3234 observed reflections with I 2σ（I）.X-ray analysis reveals that the title compound adopts a pinched cone conformation which leads to an open cavity.Intermolecular C–H O weak interactions link the molecules along the bc plane,which are effective in the stabilization of the crystal structure.     

Hydrothermal Synthesis and Structure of One New Vanadoarsenate [Zn（dien）（Hdien）]2[As6V15O42（H2O）]·4H2O

One new arsenic-vanadium cluster, [Zn（dien）（Hdien）]2[As6V15O42（H2O）]·4H2O （1, dien = diethylenetriamine）, has been hydrothermally synthesized and characterized by IR, elemental analysis, TGA, magnetic property and single-crystal X-ray diffraction analysis. Crystal data for 1： monoclinic, space group P21/n, a = 13.959（3）, b = 22.428（5）, c = 22.831（5） A^°, β = 90.733（4）°, Z = 4. X-ray crystallographic study showed that compound 1 is constructed from [As6V15O42（H2O）]^6- polyoxoanions linked together by novel [Zn（dien）（Hdien）]^3＋ complex fragments via hydrogen bonds into a three-dimensional network. Variable temperature susceptibility measurement demonstrates the presence of antiferromagnetic interaction between V^IV cations in 1.     

Hydrothermal Synthesis,Crystal Structure and Fluorescence Spectrum Studies of a Supramolecular Compound {[2-（2-Pyridyl）benzimidazoleH2]2＋ ·[SbCls]2-}2

A new supramolecular compound, { [2-（2-pyridyl）benzimidazoleH2]2＋.[SBC15]2-}2, was synthesized by the hydrothermal reaction of o-diaminobenzene, 2-pyridinecarboxylie acid and SbCl3 in 1：1 HC1 solution, and characterized by chemical analysis, elemental analysis, IR spectra, thermogravimetfic analysis and fluorescence spectra. The crystal structure was deter- mined by X-ray single-crystal diffraction. The crystal belongs to the monoclinic system, space group P211c, with a = 16.0397（13）, b = 14.3189（12）, c = 15.6370（13） A, β = 105.8980（10）°, V = 3454.0（5） A3, Z = 4, C24H22Cl10N6Sb2, Mr = 992.48, Dc = 1.909 g/cm3,/z = 2.366 mm-1, S = 1.010, F（000） = 1920, R = 0.0254 and wR = 0.0555. The coordination anion, [SbCl5]2- which is a distorted tetragonal pyramid, is composed by coordinating action with Sb3＋ ion and five adjacent chloride ions. Every four coordination anions of [SbCl5]2- form a biquaternion ring structure through the secondary bonding of Sb...Cl. Moreover, the compound adopts a three-dimensional network supramolecular structure because of the hydrogen bonds and π-π stacking between the rings and the 2-（2-pyridyl）benzimidazole divalent cations. The title compound also shows good fluorescent behaviors.     

Synthesis,Crystal Structure and Fungicidal Activity of （E）-2-[（4-tert-Butyl-5-（4-methoxybenzyl）thlazol-2 yhmino）methyl]phenol

The title compound （E）-2-[（4-tert-butyl-5-（4-methoxybenzyl）thiazol-2-ylimino）methyl]phenol was synthesized by the reaction of 5-（4-methoxybenzyl）-4-tert- butylthiazol-2-amine with salicylaldehyde, and its crystal structure was determined by single-crystal X-ray diffraction. The crystal belongs to the monoclinic system, space group P21/c with a = 5.9362（8）, b = 11.5070（15）, c = 29.460（4）A, β= 97.326（3）°, V = 1995.9（5） A^3, Z = 4, F（000） = 808, C22H24N2O2S, Mr= 380.49, De= 1.266 g/cm^3, S = 1.031,μ = 0.181 mm^-1, the final R = 0.0474 and wR = 0.1441 for 4327 observed reflections （I 〉 2σ（I））. Intramolecular O-H…N hydrogen bond is observed in the crystal. The preliminary bioassay showed that the title compound exhibits 95% inhibition rate against Rhizoctonia solani at the test concentration of 500 mg/L.