Synthesis, Crystal Structure and Properties of Complex VO（C10H9NO3） （C13H10NO2）

Complex VO(C10H9NO3)(C13H10NO2)(C10H9NO2-3=N-salicylidene-L-alaninate, C13H10NO-2=N-phenylbenzohydroxamate) was synthesized and characterized by means of elemental analysis, IR, UV, 1H NMR spectroscopies, cyclic voltammetry and single crystal X-ray diffraction. The complex crystallized in a monoclinic system with space group P21 and crystal cell parameters a=0.9720(1) nm, b=1.8274(2) nm, c=1.2542(1) nm, β=104.868(9)°, V=2.1532(4) nm3, Mr=470.34, Z=2. The two oxygen atoms and the one nitrogen atom of the tridentate Schiff base ligand and the one oxime oxygen atom of the hydroxamate ligand coordinate to the vanadium atom, forming an equatorial plane, the two axial positions are respectively occupied by the oxygen atom of the oxovanadium and the carbonyl oxygen atom of the hydroxamate and the vanadium atom exhibits a distorted octahedral VO(ONO)(OO) coordination sphere. The 1H NMR spectrum suggests that the two isomers, endo and exo in a molar ratio of 1/1.7, coexist in the solution of the title complex in CDCl3. There exists a quasi-reversible one-electron redox reaction corresponding to VⅤ/VⅥ couple in the three non-aqueous solvents, and the redox potential E1/2 of the title complex substantially shifts in the direction of the positive voltage increase in the order: CH2Cl2＜CH3CN＜DMF.     

Synthesis, Crystal Structure, Fluorescence Property and Antibacterial Activity of Two Unprecedented One-dimensional Chain Metal organic Coordination Polymers： Zn（H-SSA）（Phen）（H20）2 and Cu（H-SSA） （Phen） （H20）2

The reaction of 5-sulfosalicylic acid(H3-SSA) with o-phenanthroline(Phen),NaOH,and Mcl2(M=Zn,Cu) affords Zn(H-SSA)(Phen)(H2O)2(1) and Cu(H-SSA)(Phen)(H2O)2 (2),respectively ,compounds 1 and 2 are characterized by elemental analysis,IR,fluorescence spectra and single crystal Xray diffraction analysis.The X-ray diffraction analyses reveal that compounds 1 and 2 are isostructure.The 5-sulfosalicylic acid ligand loses two protons at the sulfo-group and carboxylic group during the reaction.The Zn(II) and Cu(II)ions are sixcoordinated and adopt distorted octahedral geometry,which are surrounded by two N atoms from Phen,two O atoms from two water molecules,one O atom from-SO3 group and one oxygen from carboxylic group of the other H-SSA.Compounds 1 and 2 have unprecedented one-dimensional linear chain formed by a repeating mononuclear structureal unit.which is bridged by H-SSA.The fluorescence intensity of 1 and 2 is stronger than that of Phen and H3-SSA at 400nm.The lowest excited single states of these complexes are assigned as mainly Phen localized 1(π π),The antibacterial activity test shows that compounds 1 and 2 strongly inhibit the growth of Streptococcus haemolyticus,Straphylococcus aureus and Escherichia coli.     

Synthesis of Substituted Indenyl Lanthanide Chloride and Molecular Structure of[（C5H9C9H6）2Yb（μ—Cl）2Li（Et2O）2]

Reaction of anhydrous ytterbium trichlorides with 2 equiv.of cyclopentylindenyl lithium in THF solution,followed by removal of the solvent and crystallization of the porduct from diethyl ether,affords a crystal complex of the composition(C5H9C9H6)2Yb(μ-Cl)2Li(Et2O)2.Crystallographic analysis shows that the ytterbium coordinated by two cyclopentylindenly rings and lithium surrounded by two ether molecules are bridged by the two chlorine atoms and Yb,Li and two chlorine atoms form a plane.     

Structure and Photosynthetic Mimicking of Bis（2,6—bis（benzimidazol—2—yl）pyridine）manganese（Ⅱ）

Mn(bzimpy)2(1)[bzimpy=2,6-bis(benzimidazol-2-yl)pyridine],a mononuclear manganese(Ⅱ）complex,was synthesized by the reaction of Mn(OOCMe)2 with bzimpy in absolute ethanol.The complex was structurally characterized by elemental analysis,cyclic voltammetry,and X-ray crystallography.In the complex,the manganese-nitrogen distances were different,and the geometry and the metal ion environment showed the distortion.The cyclic voltammetric measurements have been performed to assess its redox characteristics.The presence of oxidation wave at 0.62V and 0.081V vs.SCE or 0.8V and 1.0v vs.NHE suggested that this complex could catalyze the oxidation of water,therefore,simulate the water-oxidizing complex(WOC) of photosystem Ⅱ (PS Ⅱ).The measurements of photoreduction of 2,6-dichlorophenolindophenol (DCPIP),and oxygen evolution in the manganess-depleted and the comples 1-reconstituted PS Ⅱ preparations just support our conjecture.     

Synthesis, Characterization, Crystal Structure and Antibacterial Activities of a Nickel（Ⅱ） Complex with 2＇-（2-Thienylidene）-hydroxybenzoylhydrazide

In the ethanol solvent, a nickel(Ⅱ) complex Ni(C12H10N2O2S)2 upon reaction of 2'-(2-thienylidene)-hydroxybenzoylhydrazide with nickel acetate was synthesized, and its structure was characterized by IR, UV, elemental analysis and X-ray diffraction analysis. The crystal belongs to monoclinic system, space group C2/c with a = 22.052(3), b = 5.9681(6), c = 18.522(2) (A), β = 110.679(4)° , V = 2280.6(4) (A)3, Z = 4, Mr = 551.27, μ = 1.606 mm-1, Dc = 1.075 g/cm3, F(000) = 1136 and Rint = 0.0556. The nickel(Ⅱ) atom in the compound is four-coordinated with two nitrogen atoms from amide and two oxygen atoms from keto group. The biological activities have been measured, show- ing the compound exhibits better anti-bacterial activity than the ligand.     

Synthesis,X—Ray Structure and Characterization of a Triruthenium Cluster Complex Ru^Ⅲ3（μ3—O）（μ—CH3COO）6（py）2Cl with Four Steps One—electron Redox Processes

The synthesis and crystal structure of oxo-centered carboxylate-bridge trinuclear ruthenium complex,Ru3O(CH3OO)6(py)2Cl(py=pyridine)(1),are reported herein.The complex 1 has been characterized by IR,cyclic voltammetry (CV),UV-Vis and X-ray crystal analysis.The complex 1 in 0.1 mol/L (n-C4H9)4HPF6-CH2Cl2 solution at room temperature shows four oneelectron redox processes at E1/2=-1.38,1.20,-0.17 and 1.07V vs. Ag/AgCl.     

Synthesis and Characterization of a New Ligand 2-（4, 5-Dihydro-2-thiazolyl）-6-methoxylbenzothiazole and Its Dinuclear Co（II） Complex

A new ligand 2-(4,5-dihydro-2-thiazolyl)-6-methoxyl benzothiazole and its new dinuclear Co(II) coordination complex [Co(C11H10N2OS2)Cl2]2·2CHCl3 (1) have been synthesized and characterized. Complex 1 was synthesized by the reaction of Co(II) salt with 2-(4,5-dihydro- 2-thiazolyl)-6-methoxyl benzothiazole under room-temperature evaporation condition and struc- turally characterized by single-crystal X-ray diffraction analysis and IR spectroscopy. The supramolecular network of complex 1 is stabilized by the presence of intermolecular interaction, such as C–H···Cl hydrogen bonding and π-π stacking. The complex crystallizes in triclinic, space group P1 with a = 8.3288(12), b = 10.5273(15), c = 10.822(2), α = 93.416(3), β = 90.864(3), γ = 94.890(3)o, V = 943.60(2)3, Z = 2, Dc = 1.758 g/cm3, F(000) = 498 and μ = 1.840 mm-1. The final complex [Co(C11H10N2OS2)Cl2]2·2CHCl3 is a diplex bridged dinuclear complex consisting of two Co(II) ions, two ligands, two bridging Cl- anions and two terminal Cl- anions.     

Synthesis, Crystal Structure, UV-vis and EPR Studies of（ NH3CH2CH2NH2 ） 2.5 [ Mo0.5^（V）W0.5^（VI）O2 （ OC6H4O ） 2]

Cis-dioxo-metal complex ( NH3CH2CH2NH2 ) 2.5 [ Mo0.5^(V)W0.5^(VI)O2 ( OC6H4O ) 2] 1 was obtained by the reaction of tetra-butyl ammonium hexamolybdotungstate with 1, 2-dihydroxybenzene in the mixed solvent of CH3OH, CH3CN and ethylenediamine,and characterized by X-ray diffraction, UV-vis and EPR analysis. Compared with its analogous complexes (NH3CH2CH2NH2)3[Mo^(V)O2(OC6H40)2] 2 and (NH3CH2CH2NH2)2[W^(VI)O2(OC6H4O)2] 3, the results show that tungsten(VI) is less active in redox than molybdenum (VI) and that the change of the valence induced by substitution of W(VI) for Mo(V) in EMO2(OC6H40)2]n- does not influence the coordination geometry of the complex anion in which the metal center exhibits distorted octahedral coordination with cis-dioxo catechol. The responses to EPR of complexes 1 and 2 are active but complex 3 is silent,and the UV-vis spectra exhibited by the three complexes are obvious different because of the different electronic configuration between the central Mo(V) and W(VI) ions in the complexes.It is noteworthy that complexes 1 and 2 have the similar EPR signal to flavoenzyme, suggesting that the three complexes have the same coordination geometry feature with the co-factor of flavoenzyme.     

Synthesis and Crystal Structures of Three Ladder Distannoxane Dimers [（PhCH2）2（Cl）SnOSn（X）（CH2Ph）2]2（X=Cl,OMe,OEt）

Three distannoxane dimers[(PhCH2)2(Cl)SnOSn(X)(CH2Ph)2]2(X=Cl,OMe,OEt)were prepared by the hydrolytic reaction of (PhCH2)2SnCl2 with sodium alkoxides.The compounds are assigned tetranuclear distannoxane structures in solid state.which contain the so-called ladder arrangement with a central planar Sn2O2 four-membered ring.The endo-and exo-cyclic Sn atoms are both five-coordinate,and have distorted trigonal bipyramidal geometries.A variety of hydrolyses of(PhCH2)2SnCl2 were performed and these dimers were characterized by IR,^1H NMR spectroscopy and X-ray diffraction analysis.     

Synthesis and Structure Characterization of Aqua-（μ2-carbonato-O,O′）-（2,2′-bipyridyl）-copper（Ⅱ） Dihydrate

Under hydrothermal conditions the reaction of cis-aconitic acid with Cu2(OH)2CO3 and bipy (bipy = 2,2'-bipy) in H2O/DMF (3:2) afforded a neutral mononuclear compound [Cu- (bipy)((2-CO3)(H2O)](2H2O, which has been structurally characterized by single-crystal X-ray diffraction analysis. The crystal belongs to triclinic, space group Pī with a = 8.3950(5), b = 8.7974(5), c = 9.4496(3)（A。）, α = 98.270(3), β = 93.014(3), γ = 100.068(3)°, V = 677.83(6) （A。）3, Dc = 1.635 g/cm3, Z = 2, C11H14CuN2O6, Mr = 333.78, μ = 1.637 mm－1, λ(MoKα) = 0.71073 （A。）, F(000) = 342, the final R = 0.0616 and wR = 0.1273 for 1621 observed reflections with I > 2σ(I). The structure of the complex contains a distorted square pyramidal core with a bipy, a carbonate anion and a water molecule coordinating to a CuⅡ atom. The dihedral angle between the two planes composed of N(1)N(2)Cu(1) and O(1)O(3)Cu(1) is 21.73(8)°. The intermolecular hydrogen bonds (O…O) are observed in the crystal structure.     

Three isomeric forms of hydroxyphenyl‐2‐oxazoline: 2‐(2‐hydroxyphenyl)‐2‐oxazoline, 2‐(3‐hydroxyphenyl)‐2‐oxazoline and 2‐(4‐hydroxyphenyl)‐2‐oxazoline

Crystal structures are reported for three isomeric compounds, namely 2‐(2‐hydroxy­phenyl)‐2‐oxazoline, (I), 2‐(3‐hydroxy­phenyl)‐2‐oxazoline, (II), and 2‐(4‐hydroxy­phenyl)‐2‐oxazoline, (III), all C₉H₉NO₂ [systematic names: 2‐(4,5‐dihydro‐1,3‐oxazol‐2‐yl)phenol, (I), 3‐(4,5‐dihydro‐1,3‐oxazol‐2‐yl)phenol, (II), and 4‐(4,5‐dihydro‐1,3‐oxazol‐2‐yl)phenol, (III)]. In these compounds, the deviation from coplanarity of the oxazoline and benzene rings is dependent on the position of the hydroxy group on the benzene ring. The coplanar arrangement in (I) is stabilized by a strong intra­molecular O—H⋯N hydrogen bond. Surprisingly, the 2‐oxazoline ring in mol­ecule B of (II) adopts a ³T₄ (^C2T_C3) conformation, while the 2‐oxazoline ring in mol­ecule A, as well as that in (I) and (III), is nearly planar, as expected. Tetra­mers of mol­ecules of (II) are formed and they are bound together via weak C—H⋯N hydrogen bonds. In (III), strong inter­molecular O—H⋯N hydrogen bonds and weak intra­molecular C—H⋯O hydrogen bonds lead to the formation of an infinite chain of mol­ecules perpendicular to the b direction. This paper also reports a theoretical investigation of hydrogen bonds, based on density functional theory (DFT) employing periodic boundary conditions.     

(2E)‐N‐(2‐Iodo‐4,6‐dimethylphenyl)‐2‐methylbut‐2‐enamide

The title compound, C₁₄H₁₈INO, crystallizes as +sc/+sp/+sc 2‐iodoanilide molecules (and racemic opposites) and shows significant intermolecular I...O interactions in the solid state, forming dimeric pairs about centres of symmetry. Under asymmetric Heck conditions, the S enantiomer of the dihydroindol‐2‐one was obtained using (R)‐(+)‐2,2′‐bis(diphenylphosphino)‐1,1′‐binaphthyl [(R)‐BINAP], suggesting a mechanism that proceeds by oxidative addition to give the title (P) enantiomer of the compound and pro‐S coordination of the Re face of the alkene in a conformation similar to that defined crystallographically, except that rotation about the C—C bond of the butenyl group is required.     

Methyl 2‐acetamido‐2‐deoxy‐β‐d‐glucopyranoside dihydrate and methyl 2‐formamido‐2‐deoxy‐β‐d‐glucopyranoside

Methyl 2‐acetamido‐2‐deoxy‐β‐d ‐glucopyranoside (β‐GlcNAcOCH₃), (I), crystallizes from water as a dihydrate, C₉H₁₇NO₆·H₂O, containing two independent molecules [denoted (IA) and (IB)] in the asymmetric unit, whereas the crystal structure of methyl 2‐formamido‐2‐deoxy‐β‐d ‐glucopyranoside (β‐GlcNFmOCH₃), (II), C₈H₁₅NO₆, also obtained from water, is devoid of solvent water molecules. The two molecules of (I) assume distorted ⁴C₁ chair conformations. Values of ϕ for (IA) and (IB) indicate ring distortions towards B_C2,C5 and ^C3,O5B, respectively. By comparison, (II) shows considerably more ring distortion than molecules (IA) and (IB), despite the less bulky N‐acyl side chain. Distortion towards B_C2,C5 was observed for (II), similar to the findings for (IA). The amide bond conformation in each of (IA), (IB) and (II) is trans, and the conformation about the C—N bond is anti (C—H is approximately anti to N—H), although the conformation about the latter bond within this group varies by ∼16°. The conformation of the exocyclic hydroxymethyl group was found to be gt in each of (IA), (IB) and (II). Comparison of the X‐ray structures of (I) and (II) with those of other GlcNAc mono‐ and disaccharides shows that GlcNAc aldohexopyranosyl rings can be distorted over a wide range of geometries in the solid state.     

2‐(2‐Oxoimidazolidinyl)ethyl 2‐methyl­prop‐2‐enoate

In the crystal structure of the title compound, C₉H₁₄N₂O₃, the molecules are linked by N—H?O=C bonds into chains parallel to [001]. Large crystals are readily obtained, presumably because of the hydrogen bonds and an energetically stable conformation of the mol­ecule.     

2‐Methylphenyl 2‐methoxyacridine‐9‐carboxylate

The title compound, C₂₂H₁₇NO₃, crystallizes in the monoclinic space group P2₁/c with four molecules per unit cell. The mol­ecules are arranged in centrosymmetric pairs, joined via the C and attached H atoms in the meta position relative to the methoxy group. These pairs are bonded in the crystalline phase as a result of non‐specific dispersive interactions, and through a network of C—H?O interactions involving the non‐bonded O atom of the carboxy group and, to some extent, the O atom of the methoxy group. The methoxy substituent lies in the plane of the almost planar acridine moiety and is directed towards the phenyl ester group. The phenyl ester group itself is twisted by 35.9 (5)° relative to the mean plane of the acridine moiety.     

(E)‐2‐Methyl‐3‐(2‐methyl‐2‐nitro­vinyl)‐1H‐indole and (E)‐3‐(2‐methyl‐2‐nitro­vinyl)‐2‐phenyl‐1H‐indole

In the title compounds, C₁₂H₁₂N₂O₂, (I), and C₁₇H₁₄N₂O₂, (II), respectively, the indole rings are planar and the vinyl groups lie out of the indole planes, making dihedral angles of 33.48 (5) and 41.31 (8)°, respectively. In (II), the dihedral angle between the phenyl and indole ring planes is 32.06 (6)°. In both mol­ecules, the double bond connecting the methyl­nitro­vinyl group and the indole nucleus adopts an E configuration. Notwithstanding the differences in space group [C2/c for (I) and P2₁2₁2₁ for (II)], the mode of packing of compounds (I) and (II) is determined by similar inter­molecular N—H⋯O hydrogen‐bonding inter­actions, forming chains that run parallel to [101] in (I) and [001] in (II).     

2‐[2‐(Pyrrolidin‐2‐yl)propan‐2‐yl]‐1H‐pyrrole and its amide derivative 1‐{2‐[2‐(1H‐pyrrol‐2‐yl)propan‐2‐yl]pyrrolidin‐1‐yl}ethanone

In the title compounds, C₁₁H₁₈N₂, (II), and C₁₃H₂₀N₂O, (III), the pyrrolidine rings have twist conformations. Compound (II) crystallizes with two independent molecules (A and B) in the asymmetric unit. The mean planes of the pyrrole and pyrrolidine rings are inclined to one another by 89.99 (11) and 89.35 (10)° in molecules A and B, respectively. In (III), the amide derivative of (II), the same dihedral angle is much smaller, at only 13.42 (10)°. In the crystal structure of (II), the individual molecules are linked via N—H...N hydrogen bonds to form inversion dimers, each with an R²₂(12) graph‐set motif. In the crystal structure of (III), the molecules are linked via N—H...O hydrogen bonds to form inversion dimers with an R²₂(16) graph‐set motif.     

An Efficient Synthesis of 3‐(3‐benzyl‐2‐(phenylimino)‐2,3‐dihydrothiazol‐4‐yl)‐6‐methyl‐4‐(2‐oxo‐2‐phenylethoxy)‐3,4‐dihydro‐2H‐pyran‐2‐one Derivatives via Multi‐Component Approach

An easy, highly efficient and a new convenient one‐pot, two‐step approach to the synthesis of 3‐(3‐benzyl‐2‐(phenylimino)‐2,3‐dihydrothiazol‐4‐yl)‐6‐methyl‐4‐(2‐oxo‐2‐phenylethoxy)‐3,4‐dihydro‐2H‐pyran‐2‐one is described. These compounds were synthesized from 3‐(3‐benzyl‐2‐(phenylimino)‐2,3‐dihydrothiazol‐4‐yl)‐4‐hydroxy‐6‐methyl‐3,4‐dihydro‐2H‐pyran‐2‐one and α‐bromoketones in good yields. The compounds 4 were synthesized by a multi‐component reaction between 1 , 2 , and 3 and the prominent features of this protocol are mild reaction conditions, operation simplicity, and good to high yields of products.     

First synthesis of 2‐(2,4,4‐trimethyl‐3,4‐dihydro‐2H‐benzo[h]chromen‐2‐yl)‐1‐naphthol and 3‐(2,4,4‐trimethyl‐3,4‐dihydro‐2H‐benzo[g]chromen‐2‐yl)‐2‐naphthol from 1‐ and 2‐naphthol derivatives

Two new structurally isomeric, 2‐(2,4,4‐trimethyl‐3,4‐dihydro‐2H‐benzo[h]chromen‐2‐yl)‐1‐naphthol ( 1 ) and 3‐(2,4,4‐trimethyl‐3,4‐dihydro‐2H‐benzo[g]chromen‐2‐yl)‐2‐naphthol ( 3 ) have been synthesized from 2‐acetyl‐1‐naphthol and ethyl‐3‐hydroxy‐2‐naphthoate, respectively, involving Grignard reaction, dehydration of the corresponding tertiary alcohols, and hetero Diels–Alder dimerization. The two benzochromenes ( 1 and 3 ) have been fully characterized by IR, NMR, and HRESIMS data. Their structures are further supported by crystallography of their corresponding acetates ( 2 and 4 ). J. Heterocyclic Chem., (2011).