‘Whole-molecule Disorder’ Refinement of 4-（4-Hydroxybenzylideneiminio）phenol Hemichloride Hemihydroxide

The two independent cations of the salt, [HO-C6H4-CH=NH-C6H4-OH]·1/2OH·1/2Cl, are both disordered about an axis connecting the two oxygen atoms at the para-positions of the aromatic rings, the disorder being in a 83:17 ratio in one cation and 91:9 in the other. The hydroxide and chloride anions are ordered. The treatment of the nearly ‘whole-molecule disorder’ by employing a small number of restraints is described. Crystal data: C13H12.5Cl0.5NO2.5, triclinic, P , a = 9.1731(4), b = 9.2048(4), c = 15.9144(7) , α = 104.822(1), β = 90.077(1), γ = 118.641(1)o and V = 1127.86(9) 3 at –173 K.     

Two Polymorphs of the Inclusion Compound [（n-C4H9）4N] ＋（C13H9O3）-H2O

Two polymorphs of the inclusion compound [(n-C4H9)4N]+·(C13H9O3)-·H2O havebeen prepared and characterized by X-ray crystallography. Polymorph 1: triclinic P 1 , a =13.4982(2), b = 13.5743(2), c = 17.1996(2) , α = 67.045(1), β = 77.845(1), γ = 88.762(1)°, V =2830.43(7)3, Z = 4, R = 0.0491, wR = 0.1276; Polymorph 2: tetragonal P43, a = b = 13.53690(1) , c = 30.8491(8) , V = 5653.02(16)3, Z = 8, R = 0.0448, wR = 0.0984. In these two crystalstructures, the hydrogen-bonded ribbons built of 4,4 -dihydroxybenzophenone (DHBP, C13H10O3)anions and water molecules are orderly arranged to generate two-dimensional host layers, withtetrabutylammonium cations contained between the layers to form the sandwich-like inclusioncompounds. The structures of 1 and 2, which exist as two polymorphs, both display the similarpacking pattern and hydrogen-bond linking model.     

Synthesis and Crystal Structure of Bis[O,O'-di(2-phenylethyl)dithiophosphato](α,α'-bipyridine)copper(Ⅱ)

A ternary adduct Cu[S2P(OCH2CH2Ph)2]2·bipy(bipy=α,α'-bipyridine) was syn-thesized and characterized by elemental analysis,IR and single-crystal X-ray diffraction.The crystal belongs to the triclinic system,space group P1 with a=10.2320(2),b=11.5249(3),c=18.0916(3),α=98.95(1),β =103.601(1),γ=91.272(2)°,V=2044.49(7)3,Z=2,Dc=1.453 g/cm3,T=153(2) K,C42H44CuN2O4P2S4,Mr=894.51,λ(MoKα)=0.71073,μ=0.86 mm-1,S=0.999,(△/σ)max=0.002,the final R=0.0243 and wR=0.0704.A total of 9221 unique reflections were collected,of which 8573 with Ⅰ 2σ(Ⅰ) were observed.The Cu(Ⅱ) atom is five-coordinated in a rather distorted trigonal bipyramidal geometry(τ value=0.537).The Cu-S distances range from 2.3491(4) to 2.4829(4) ,and the Cu-N distances are 1.9987(12) and 2.0584(11) ,respectively.An interesting feature of this adduct resides in its two-dimensional(2D) open framework constructing through hydrogen bonding and π-π interactions.     

Syntheses and Crystal Structures of 4,4‘—Diformyl—diphenoxyethane and 4,4’,4‘’—Triformyl—triphenoxytriethylamine

Two title compounds, 4,4'-diformyl-diphenoxyethane (compound 1, C16H14O4)and 4,4',4'-triformyl-triphenoxytriethylamine (compound 2, C27H27NO6), were synthesized by condensation of 4-hydroxybenzaldehyde with 1,2-dichloroethane and tris2-chloroethylamine, respectively in dimethyl formamide in the presence of anhydrous potassium carbonate. The crystal data are: monoclinic, P21/c, a = 7.571(2), b = 12.608(3), c = 7.357(2) ', = 105.823(6)o, V = 675.7(2)'3, Mr = 270.3, Z = 2, Dc = 1.328 g/cm3, F(000) = 284, (MoK = 0.096 mm-1, R = 0.0537 and wR = 0.2189 for compound 1; and monoclinic, P21/n, a = 11.7162(6), b = 9.0042(6), c = 22.908(2) ', = 99.505(1)°, V = 2383.5(3) '3, Mr = 461.50, Z = 4, Dc = 1.286 g/cm3, F(000)= 976, (MoK = 0.091 mm-1, R = 0.0464 and wR = 0.1462 for compound 2. The molecule of compound 1 dialdehyde is located at the crystallographic inversion center nearby the midpoint of C8-C8A single bond. The three chains in the molecule of compound 2 trialdehyde are of non-crystallographic pseudo-C3 symmetry, and each of them is quite planar.     

Synthesis and Crystal Structure of N-[（3aR,4R,4aR,5aS,6S,6aS）-1,3-Dioxooctahydro-4,6-ethenocyclopropa[f]isoindol-2（1H）-yl]-3-（trifluoromethyl）phenylmethanimine

The crystal structure of the title compound(C19H15F3N2O2,Mr = 360.33) was determined by single-crystal X-ray diffraction.The crystal belongs to triclinic,space group P1,with a = 6.5604(7),b = 13.9614(16),c = 18.1790(18) ,α = 102.749(7),β = 97.542(6),γ = 94.355(4)°,V = 1600.5(3) 3,Z = 4,Dc = 1.495 g/cm3,λ(MoKα) = 0.71070,F(000) = 744,μ(MoKα) = 0.122 mm-1,R = 0.0434 and wR = 0.1051.A total of 7590 unique reflections were collected,of which 5429 with |F|2 ≥ 2σ|F|2 were observed.The two cyclohexene rings in the molecule adopt boat-boat conformations with the deviations of ring atoms C(9) and C10 from the C(5)/C(6)/C(7)/C(8) plane(Ⅰ) by 1.1204(0.0023) and 1.1132(0.0023) ,respectively,whereas from the C(2)/C(3)/C(5)/C(8) plane(Ⅱ) by 1.1627(0.0022) and 1.1818(0.0021) ,respectively.In the cyclopropane and lactam rings,atoms C(11) and N(1) point towards the double bond of C(9)-C(10) and the dihedral angle between the ring plane(Ⅲ) containing C(1),C(2),C(3) and C(4) and plane(IV) consisting of C(6),C(7) and C(11) is 55.76(0.07)°.The dihedral angles between planes Ⅳ and Ⅰ and Ⅱ and Ⅲare 63.58(0.07)° and 58.10(0.06)°,respectively.The dihedral angle between the benzene ring C(13)～ C(18) and plane Ⅳ is 42.41(0.06)°.     

Synthesis and Antibacterial Activity of 8-Substituted Phenyl-1-pyridin-3-yl-5H-bis[1, 2, 4]triazolo[3, 4-b； 4＇, 3＇-d][1, 3, 4] thiadiazines

To find new structural leading compounds for the research of the multidrug resistant of antibacterial agents, five novel 8-substituted phenyl-l-pyridin-3-yl-5H-bis[1, 2, 4] triazolo[3, 4-b;4‘,3‘-d] thiadiazines were prepared from the corresponding intermediates of 3-(5-substituted phenyl[1,3,4]oxadiazol-2-ylmethylsulfanyl)-5-pyridin-3-yl-[1,2,4]triazol-4-ylamines via intramolecular cyclization and the antibacterial activity in vitro against Gram-postive (G^ ) and Gramnegatiye (G) bacteria was primarily evaluated.     

Synthesis and Crystal Structure of the Azo Copper（Ⅱ）-complex

The single crystals of the azo copper(Ⅱ)-complex have been obtained from the solution of the compound dissolved in the ethanol by slow evaporation at room temperature. The structure was successfully determined by single-crystal X-ray diffraction. The crystal is of triclinic system, space group P1 with a = 7.8843(12), b = 11.5998(17), c = 13.955(2) , α = 112.214(2), β = 95.105(2), γ = 97.616(2)o, V = 1157.6(3) 3, Mr = 586.97, Z = 2, F(000) = 600, Dc = 1.684 g/cm3, μ(MoKα) = 1.120 mm-1, the final R = 0.0419 and wR = 0.1259 for 3475 observed reflections with I > 2σ(I). The coordination around copper(II) atom is a slightly distorted square-pyramidal geometry involving [Cu(C16H11N4O8S)(OH)H2O]-cation, one Na+ anion and one C2H5OH solvate molecule. The hydrogen bonds and π···π stacking interactions extend the complex into a three-dimensional framework.     

Syntheses and Crystal Structures of Two Heterobimetallic Clusters [WOS_3Cu_3I(dmpzm)_2]·2(MeCN)_(0.5) and [WS_4Cu_4I_2(dmpzm)_2]·DMF(dmpzm=Bis(3,5-dimethylpyrazolyl)methane)

The reaction of [Et4N]2WOS3 with three equiv.of CuI and dmpzm in MeCN afforded [WOS3Cu3I(dmpzm)2]·2(MeCN)0.5(1·2(MeCN)0.5) while that of [PPh4]2WS4 with four equiv.of CuI in DMF/MeCN followed by the addition of two equiv.of dmpzm in MeOH gave rise to [WS4Cu4I2(dmpzm)2]·DMF(2·DMF).Both compounds were characterized by elemental analysis,IR,and single-crystal X-ray diffraction analysis.1·2(MeCN)0.5 crystallizes in triclinic,space group P1-with a = 11.4552(5),b = 11.6735(3),c = 16.2278(9) ,α = 99.537(9),β = 101.986(2),γ = 118.464(13)o,V = 1775.5(3)3,Z = 2,μ = 6.080 mm-1,Dc = 1.983 Mg/m3,T = 193(2) K,C24H35Cu3IN9OS3W,Mr = 1063.22,F(000) = 1018,S = 1.060,R = 0.0376 and wR = 0.0870.2·DMF belongs to the orthorhombic system,space group Pmn21 with a = 22.145(4),b = 11.464(2),c = 7.7370(15) ,V = 1964.2(6)3,Z = 2,μ = 6.865 mm-1,Dc = 2.189 Mg/m3,T = 193(2) K,C25H39Cu4I2N9OS4W,Mr = 1301.72,F(000) = 1226,R = 0.0632,wR = 0.1706 and S = 1.130.1·2(MeCN)0.5 consists of one CuI and two [Cu(dmpzm)]+ fragments that are linked by [WOS3]2-species via six Cu-S bonds,forming a nido-like [WS3Cu3] core.2·DMF contains a saddle-shaped [WS4Cu4] core with two iodides coordinated at two Cu centers in a cis position and two dmpzm ligands being chelated at another two Cu centers in a cis position.     

Crystal and Molecular Structure of Ethyl 2-[（4-Hydroxy-phenyl）hydrazono]-3-oxobutanoate

The title compound,C 12 N 2 O 4 H 14 (M r=250.3),crystallizes in triclinic P1 space group with a=7.7709(9),b=8.7534(11),c=9.6958(12),α=77.103(2),β=80.496(2),γ=86.726(2)o,V=633.9(1) 3,Z=2,F(000)=264,D c=1.311 Mg/m 3,μ(MoKα)=0.1 mm-1,the final R=0.056,and wR=0.15 for 2239 observed reflections (I > 2σ(Ⅰ)).The molecules in the crystal are linked through O-H···O type of hydrogen bonding interaction forming an infinite chainlike structure.The phenylhydrazone ring and oxobutanoate groups are almost planar.The keto hydrazo group adopts a Z-configuration in the molecule and the torsion angle is-177.6(2)°.     

Synthesis and Crystal Structure of 2-（4-Chlorophenyl）-1,4,5-triphenyl-1H-imidazole

The compound 2-(4-chlorophenyl)-1,4,5-triphenyl-1H-imidazole(1,C27H19ClN2) has been synthesized and its crystal structure was determined by single-crystal X-ray diffraction.The crystal of 1 belongs to the triclinic system,space group P with a = 10.3350(19),b = 10.238(2),c = 11.201(2) ,α = 85.957(16),β = 83.148(15),γ = 66.467(15)°,V = 1078.5(4) 3,Mr = 406.89,Z = 2,F(000) = 422,Dc = 1.257 g/cm3,μ = 0.193 mm-1,T = 298(2) K,S = 1.092,R = 0.0702 and wR = 0.1258.The imidazole ring system is planar and makes a dihedral angle of 40.3° with the chlorobenzene ring.     

Synthesis and X-ray Structural Studies of 2-（2-Benzofuroylimino）-3-aryl-4-phenyl- 1,3-thiazolines

The synthesis for acyliminothiazolines by treatment of N, N□-substituted thioureas with α-bromoacetophenone under aqueous media was described. 2-（2-Benzofuroylimino）-3-aryl- 4-phenyl-1,3- thiazolines were characterized by infrared, NMR spectroscopy and elemental analysis. The single crystals of compounds 4a and 4b were grown by slow evaporation of 80% ethanol solution at room temperature. Compounds 4a and 4b crystallize in triclinic space group P1 and monoclinic space group P21/c, respectively.     

Triheterocyclic Thiadiazepine Derivatives of Pharmacological Interest： Synthesis of 2-Aryl-4-[ρ-（2,3-dihydro-5-methyl-2-oxo-1,3,4-oxadiazol-3-yl）phenyl]-6-（u n）su bstituent-1 ＂,2＂ ,4＂- triazolo[3＂,4＂-b]-1 ＇,3＇,4＇-thiadiazepine

Synthesis of novel thiadiazepine derivatives based on the reactivity of 4-acetylphenylsydnone （1） was reported. The structures of the newly synthesized compounds have been proved by their physical, analytical, IR, 1^H NMR, 13^C NMR and mass spectral data.     

Construction of a Ytterbium Supramolecular Compound from 5,5＇-（Buta-diyne- 1,4-diyl）diisophthalic Acid

A novel 3D ytterbium supramolecular compound, [Yb（HBDDC）（H20）4]·2H2O（1）, was synthesized via 5,5＇-（buta-diyne-1,4-diyl）diisophthalic acid ligand（HaBDDC） under solvothermal conditions. Single-crystal X-ray diffraction analysis reveals that compound 1 crystallizes in triclinic system, PT space group with a=0.71372（14） nm, b=1.0566（2） nm, c=1.7969（4） nm, a=101.01（3）°, β=98.15（3）°, γ=99.17（3）° and V=1.2922（4） nm3. Compound 1 exhi- bits a special infinite 1D chain, which stacks parallel each other in an ABAB sequence, leading to the formation of a 3D supramolecular structure owing to the strong π-π interactions between adjacent phenyl ring groups. Moreover, compound 1 manifests excellent luminescent property.     

Synthesis,Structure and Luminescent Property of an Europium(Ⅲ) Coordination Polymer

A novel europium(Ⅲ) coordination polymer, [Eu3(pydc)3(SO4)(H2O)5(ox)0.5]·3H2O(1, H2 ox = oxalic acid, H2 pydc = pyridine-2,6-dicarboxylic acid), has been synthesized hydrothermally from the self-assembly of lanthanide ions(Eu3+) with the flexible oxalic acid and the rigid pyridine-2,6-dicarboxylic acid ligands, respectively. It crystallizes in the triclinic system, space group P1 with a = 11.225(4), b = 12.390(5), c = 13.752(5)A, α = 89.228(7), β = 71.142(6), γ = 75.552(6)°, Dc = 2.317 g/cm3, μ = 5.480 mm-1, F(000) = 1150, Z = 2, the final R = 0.0351 and w R = 0.0949 for 8782 observed reflections with I 2σ(I). Structural analysis reveals that complex 1 exhibits a three-dimensional metal-organic framework via π-π stacking interactions. In addition, complex 1 displays a red fluorescence emission in the solid state at room temperature, which corresponds to the 5D0 → 7F2 transition of Eu3+ ions.     

Synthesis and Crystal Structure of a Cr（Ⅲ） Dimer [Cr2（8-hqn）2Cl4（H2O）2]·2（CH3）2CO （8-hqn = 8-Hydroxyoxyquinolate）

The title complex [Cr2（8-hqn）2Cl4（H2O）2]·2（CH3）2CO （8-hqn = 8-hydroxyoxyquinolate） has been synthesized and characterized by single-crystal X-ray diffraction. It crystallizes in the triclinic system, space group P^-1 with a = 8.719（1）, b = 9.226（1）, c = 9.717（1） A^°, α = 71.916（2）, β= 78.072（2）, γ = 76.014（2）°, V= 713.72（15） A^°^3, Z= 1, Dc= 1.597g/cm^3, F（000） = 350 and μ（MoKa） = 1.177 mm^-1, the final R = 0.0490 and wR = 0.1055 for 1616 observed reflections with I 〉 2σ（I）. It is a dimer constructed by two monomeric units [Cr（8-hqn）Cl2（H2O）] bridged by phenoxide-like oxygen atom from 8-hydroxyoxyquinolate, where the two six-coordinated Cr（Ⅲ）atoms exhibit an octahedral coordination geometry.     

Synthesis,Crystal Structure and Thermal Stability of Complex [Cu（C_（14）H_（10）O_4）（C_（12）H_8N_2）_2]·2H_2O

The title complex has been synthesized with 2,2'-biphenyl dicarboxylic acid and 1,10-phenanthroline(phen)in the solvent mixture of water and methanol.It crystallizes(C38H28CuN4O6,Mr = 700.1)in triclinic,space group P1 with a = 1.0868(2),b = 1.2175(2),c = 1.6206(3)nm,α = 110.161(2),β = 102.605(3),γ = 93.667(2)o,V = 1941.6(6)nm3,Dc = 1.198 g/cm3,Z = 2,F(000)= 722,R = 0.0558 and wR = 0.1208.The crystal structure shows that the copper atom is coordinated with one oxygen atom from 2,2'-bphenyl dicarboxylic acid molecule and four nitrogen atoms from two 1,10-phenanthroline molecules,forming a distorted square-pyramidal coordination.The TG analysis shows that the title complex is stable under 160.0 ℃.     

Synthesis,Crystal Structure and Prosperities of 10-（4,5-Dibenzylthio- 1,3-dithiol-2-ylidene）anthracen-9（10H）-one

The title compound 10-（4,5-dibenzylthio-1,3-dithiol-2-ylidene）anthracen-9（10H）- one （C31H22OS4） has been synthesized, and its crystal structure was prepared by crystallization from CH2Cl2-MeOH. The crystal belongs to the triclinic system, space group Pi with a = 10.9758（3）, b = 11.4241（4）, c = 11.7460（2）A^°, α = 62.379（2）, β = 81.227（3）, γ = 80.321（2）°, Mr = 538.73, V = 1281.69（7） A^°^3, Z = 2, Dc = 1.396 g/cm^3, F（000） = 560,μ = 0.395 mm^-1, the final R = 0.0291 and wR = 0.0739. The molecular structure is severely distorted from planarity. The central ring of anthraquinone moiety adopts a boat conformation, while the two outer benzene rings are tilted in the opposite direction to form a dihedral angle of 23.65°. The photocurrent generation was measured and an anodic photocurrent response was obtained. The electronic spectrum was studied by using TDDFr method on the basis of optimized geometries with B3LYP method. The obtained results are in good agreement with the experimental values.     

Synthesis and Crystal Structure of （Z）-1- （3-Fluorobenzyl）-5-（（3-fluorobenzylimino）（2-hydroxy-4-methoxyphenyl）methyl）pyridin-2（1H）-one

The title compound （Z）-1-（3-fluorobenzyl）-5-（（3-fluorobenzylimino）（2-hydroxy-4- methoxyphenyl）methyl）pyridin-2（1H）-one （C27H22F2N2O3,Mr = 460.47） was synthesized and crystallized. The crystal belongs to the triclinic system,space group P1 with a = 9.951（6）,b = 10.059（6）,c = 12.927（7）A,α = 109.828（7）,β = 102.304（7）,γ = 104.898（7）°,Z = 2,V = 1110.2（11）A^3,Dc =1.377 Mg/m^3,μ（MoKα） = 0.102 mm^-1,F（000） = 480,the final R = 0.0449 and Rw = 0.1250 for 4595 observed reflections （I 〉 2σ（I））. X-ray analysis reveals that both m-fluorobenzyl groups are diorientationally disordered because of the rotation of C–C single bond which was represented as F（1）,F（2） and F（1＇）,F（2＇）. The diorientational disorder was refined and gave the occupancies of 0.665（4） and 0.335（4） for F（1） and F（1＇）,0.631（3） and 0.369（3） for F（2） and F（2＇）. Hydrogen bonds existing in the cell link different components to stabilize the crystal structure. The active data proved that the title compound has good anti-HBV activity.