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 Crystal Structure of N-[(3aR,4R,4aR,5aS,6S,6aS)-1,3-Dioxooctahydro-4,6-ethenocyclopropa[f]lisoindol-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 P(1), with a = 6.5604(7), b = 13.9614(16), c = 18.1790(18) (A), α = 102.749(7),β = 97.542(6), γ = 94.355(4)°, V= 1600.5(3) (A)3, Z = 4, Dc = 1.495 g/cm3, λ(MoKα) = 0.71070, F(000) = 744, μ(MoKα) = 0.122mm-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) (A), respectively, whereas from the C(2)/C(3)/C(5)/C(8)plane (Ⅱ) by 1.1627 (0.0022) and 1.1818 (0.0021) (A), 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 Ⅲ are 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)°.     

Optical Rotatory Feature of （R or S）—1,1’—Binaphthalene—2,2’—diol（BINOL）in various Solvents

The changes of the specific rotation and sign of optically active BINOL have been studied in polar/non-polar solvents and at the different pH values of solvent.It is considered that these changes are determined by the equilibriurn studies between cisoid and transoid conformations of BINOL with the same configuration(R or S) which related to the change of the dihedral angle between two naphthalene ring planes of BINOL.     

Synthesis and Crystal Structure of Tri—（2—mercaptopyridine N—oxide）bis（dimethyl sulfoxide） Dysprosium（Ⅲ）

A range of rare earth metal complexes of 2-mercaptopyridine N-oxide (Hmpo) have been synthesized, and studied by elemental analysis and IR spectroscopic technique. Crystal structure of Dy(mpo)3(DMSO)2 (DMSO = dimethyl sulfoxide) has been determined. The complex crystallizes in the triclinic system, space group Pī with lattice parameters: a = 9.602(3), b = 9.803(3), c = 15.498(5)A, α= 89.51(1), β= 85.73(1), γ= 62.99(1)°, Dc = 1.787 g/cm3, C19H24N3O5S5Dy, Mr = 697.21, Z = 2, F(000) = 690, μ = 3.321mm-1, the final R = 0.0237 and wR = 0.0587 for 4116 reflections with I>σ2(I). The coordination number of dysprosium Ⅲ is eight, and its coordination geometry is a somewhat distorted square antiprism with O(3), O(4), O(5), S(3) and O(1), O(2), S(1), S(2) at the tetragonal bases (dihedral angle between their mean planes is 2.9(1)0). Around the Dy atom, three five-membered ring planes (Dy, O, N, C, S) make the dihedral angles of 74.42, 11.31 and 83.72, respectively.     

Synthesis, structure and photochemical properties of r-1, c-2, t-3, t-4-tetra[2-(5-phenyloxazolyl)]cyclobutane

It was found that the main reason why trans-1, 2-bis [2-(5-phenyloxazolyl) ] ethene (POEOP) has low laser conversion efficiency is that POEOP photodimerized easily with high stereoselectivity. The photodimer r-1, c-2, t-3, t-4-tetra [2-(S-phenyloxazolyl) ] cyclobutane (TPOCB) was synthesized and its crystal structure was determined by X-ray diffraction method. The crystal is monoclinic. The space group is C2/c, with 0 = 2.2289(4), b=0.5406(2), c=2.631 7(7) nm, β=99.38(2)°, Z=4. The molecular cell of TPOCB is centrosymmetric. The dihedral angle between benzene and oxazole ring planes is similar to that of POEOP. It was also found that the photodimerization of POEOP and the photolysis of TPOCB is reversible, increasing the concentration of POEOP is advantageous to photodimerization. In contrast, decreasing the concentration of POEOP is advantageous to photolysis of TPOCB.     

CRYSTAL STRUCTURE OF THE METHYL 4—（N—（1—OXYPROPYL）—N—PHENYLAMINO]—1—[2—（2—THIENYL）ETHYL]—4—PIPERIDINECARBOXYLATE（R31826）HYDROCHLORIDE

<正> C22H28N2O3S.HCl, Mr = 436.9, triclinic,P1;a=8.557(3),b= 10.299(2),c= 13.894(2)A;α= 99.25(1),β=86.64(2),γ= 107.68(2)°;V= 1151.2(3)A3,Z= 2, DC = 1.27g/cm3,R=0.064. The torsion angle C(14)-C(1)-N(2)-0(19) in the title compound is 137.5 being much larger than that (106°) in R30730. The dihedral angle between mean planes of the thiophene ring and piperidine ring is about 83 .     

Cyanido-bridged one-dimensional systems assembled from [ReⅣCl4（CN）2]2- and [MⅡ（cyclam）]2+ （M=Ni,Cu） precursors

Three new cyanido-bridged heterometallic ReIVNiII and ReIVCuII one-dimensional systems were synthesized and extensively characterized both structurally and magnetically. Single-crystal X-ray diffraction analysis revealed that these compounds display a common topology, with chains composed of alternating [ReⅣCl4(CN)2]2- and [MⅡ(cyclam)]2+ (M = Ni in 1, Cu in 2) or [CuⅡ(N,N′-dimethylcyclam)]2+ (in 3) building units. Two different chain orientations with a tilt angle of ca. 51° to 55° are present in the crystal packing of these compounds. The magnetic susceptibility measurements suggest the presence of intrachain ferromagnetic interactions between the S = 3/2 ReIV centers and the 3d metal ions: S = 1 NiII or S = 1/2 CuII. At low temperature, a three-dimensional ordered magnetic phase induced by interchain antiferromagnetic interactions (antiferromagnetic for 1 and 2; canted antiferromagnetic for 3) is detected for the three compounds.     

Synthesis and Characterization of syn-[(η~5-C_5Me_5)_2W_2(S)_2(μ-S)_2].0.5anti-[(η~5-C_5Me_5)_2W_2(S)_2(μ-S)_2]

1 INTRODUCTION The complexes of syn- or anti-[(5-C5Me5)2- W2(S)2(-S)2] could be prepared in several ways[1~5]. For example, a mixture consisting of [Et3NH][(5-C5Me5)WS3] and anti-[(5-C5Me5)2- W2(S)2(-S)2] was generated from the reactions of [(5-C5Me5)WCl4] with H2S in the presence of NEt3[2]. The reactions of [(5-C5Me5)W(NO)I2] with H2S led a mixture of [(5-C5Me5)W(S)(S2)I] and anti-[(5-C5Me5)2W2(S)2(-S)2][3]. [(5-C5Me5)W- (StBu)3] was degraded in THF at room temperat…     

CRYSTAL STRUCTURE OF 2-(PHENYLAMINO THIOFORMYD-3,4,5,6-TETRAHYDROPYRIMIDINE

<正> The title compound 2-(phenylamino thioformyl)-3,4,5,6-tetrahy-dropyrimidine(C11H13N3S,Mr=219)was synthesized by the reaction of N,N'-diphenyl dithiooxamide with 1,3-diamine trimethylene.The crystal is monoclinic,space group P21,with unit cell constants a=6.253(1),b=7.304(1),c=12.027(2)A,β=102.71(1)°,Z=2,V=535.9(2)A3,Dc=1.35.g/cm3.The final deviation factor R=0.025.The result reveals that the dihedral angle between the thio-formyl group [S,C(7),C(8),N(1)]and the phenyl ring is 33.4°,and the thio-formyl group and the mean plane of the atoms [N(3),C(8),N(2),C(9)]are nearly coplanar.     

SYNTHESIS AND CRYSTAL STRUCTURE OF DINUCLEAR IRON CARBONYL DERIVATIVE (μ-SC_6H_5) (μ-P (SC_6H_5)_2) Fe_2 (CO)_5 (P-(SC_6H_5)_3)

<正> The reaction of Fe3(CO)12 with P(SPh)3 yields the tile compound. C41H30Fe2O5P2S6, Mr = 968. 65, monoclinic, space group, P21/n, a = 14. 449(9), b = 18. 046(11), c=16.871(10)(?), β=98. 76°, V = 4348(?)3, Z = 4, Dc=1. 480g/ cm3, λ(MoKα) = 0. 71073(?) The structure was determined by direct methods and difference Fourier syntheses and refined by full-matrix least-squares procedure to R = 0.084, Rw = 0.144 for 4059 reflections. Fe(1)-Fe(2) = 2. 576(6), Fe(2)-P(2) = 2.194(9)(?). The dihedral angle between the Fe(l)SFe(2) and Fe(1)PFe(2) planes is 81. 9°. The other one (dihedral angle between SFe(1)P and SFe(2)P planes) is 75. 2°.     

2-取代苯亚胺基噻唑烷类化合物的晶体结构研究

A series of 2-phenyliminothiazolidines has been successfully synthesized; and 2-(2-methylphenyl) iminothiazolidine (I a) and 2-(4-methylphenyl) iminothiazolidine (I b) have been selected to determine their crystal structures by X-ray diffraction technique,from their molecular graph of it is shown that double bond at 2-carbon atom of the heterocycle is all extro-cychc at the crystal state,and there are two main plaines in I a and I b.But in I a ,the angle between the planes is 61.4° and in I b the angle is about 41.4°.And so there is a strong conjugative effect in I b than in I a.So it is thought that the difference in fungicidal activities between 2-substitutedphenyl compounds (I a) and 4-substitutedphenyl compounds(I b) is due to their space factors.     

Synthesis and structure of linear hexanuclear manganese (Ⅱ)benzoate cluster

From a reaction system including benzoic acid and Mn(NO3)2 in alkali medium, two hexanuclear manganese benzoate cluster compounds have been synthesized. A compound [Et4N]2[Mn6(PhCOO)14] has been structurally characterized, which contains hexanuclear Mn11 moieties extending unlimitedly to form one-dimensional linear structure. Carboxyl oxygen atoms are bridged in variety of modes to the Mn atoms, forming an arrangement like a sinusoid for the Mn atoms. The structural parameters of these compounds were compared with the data obtained from EXAFS determination for the Mn cluster in the OEC of PS11, supporting that the coordination sphere of the Mn site in the OEC may contain carboxyl bridges. The possible combination modes between the carboxyl group and the Mn atoms have been suggested. The NMR signals exhibit widening and shift produced by the influence of the paramagnetic Mn" sites. The red-shift of the absorption in IR spectrum was observed to be attributed to the coordination of the carboxyl group to the Mn     

CRYSTAL STRUCTURE OF 6-ETHOXY-5,6-QIHYDROCHELERYTHRINE

<正> C23H23O5N Mr = 393.44, triclinic,space group P 1, a =7.659(3), b= 10.183(10), c=13.396(2)A,α=92.21(7),β=100.86(2),γ=108.16(7)°,Z=2.The structure was solved by direct methods and refined to a final R factor of 0.055, Rw=0.050). The title compound belongs to the alkaloid of benzoheterophenanthrene, the molecule possesses two conjugation planes which are proped up by N(5)-C(6) bond and the dihedral angle is 12.74(24)°.     

Synthesis and photovoltaic properties of low bandgap dimeric perylene diimide based non-fullerene acceptors

Non-fullerene organic acceptors have attracted increasing attention in recent years. One of the challenges in the synthesis of non-fullerene organic acceptors is to tune the absorption spectrum and molecular frontier orbitals, affording low bandgap molecules with improved absorption of the near-infrared solar photons. In this paper, we present the synthesis, optoelectronic and photovoltaic properties of a series of dimeric perylene diimide(PDI) based non-fullerene acceptors. These PDI dimers are bridged by oligothiophene(T) from 1T to 6T. With the increase of the oligothienyl size, the highest occupied molecular orbital(HOMO) energy is raised from ?5.65 to ?5.10 e V, while that of the lowest unoccupied molecular orbit(LUMO) is kept constant at ?3.84 e V, affording narrow bandgap from 1.81 to 1.26 e V. The absorption from the oligothiophene occurs between 350 and 500 nm, which is complementary to that from its bridged PDI units, leading to a wide spectral coverage from 350 to 850 nm. The optimal dihedral angle between the bridged two perylene planes is dependent on the oligothienyl size, varying from 5° to 30°. The solubility of the dimers depends on the oligothienyl size and can be tuned by the alkyl chains on the bridged thienyl units. The possible applications as the solution-processable non-fullerene organic acceptor is primarily studied using commercial P3 HT as the blend donor. The photovoltaic results indicate that 1T, 4T and 6T all yield a higher efficiency of ?1.2%, whereas 2T, 3T and 5T all give a lower efficiency of 0.5%. The difference in the cell performance is related with the tradeoff between the differences of absorption, HOMO level and film-morphology between these dimers.     

Synthesis, Structure and Catalytic Activity Comparison of Tris- and Tetracoordinated Lanthanide Amides

Tetracoordinated lanthanide amides [(MeaSi)2N]3Ln (μ-C1)Li(THF)3 (Ln=La (1), Pr (2)) were synthesized by the reaction of anhydrous lanthanide(Ⅲ) chlorides LnCl3 (Ln=La, Pr) with 3 equiv, of lithium bis(trimethylsilyl)amide (Me3Si)2NLi in THF, followed by recrystallization from toluene. Sublimation of 1 and 2 afforded the triscoordinate lanthanide amides [(Me3Si)2N]3Ln (Ln=La, Pr). The crystal structure of 2 was determined by X-ray diffraction analysis. The catalytic activity studies show that the tetracoordinate amides can be used as single-component MMA (methyl methacrylate) polymerization catalysts, while the triscoordinate amides showed poor activity on MMA polymerization under the same conditions.     

STUDIES ON BINUCLEAR COMPLEXES.CRYSTAL AND MOLECULAR STRUCTURE OF [Pd(μ-Ph_2Ppy)Cl]_2·0.3CH_2Cl_2

<正> [Pd(u-Ph2Ppy)Cl]2.0. 3CH2C12, Mr = 835. 70, monoclinic, space group C2/c with a=30. 405(4), b= 17. 868(2),c=12. 955(2) A,B=98. 40(1) ,V = 6962. 6A3;Z=8,Dx=1. 59 g/cm3,final R=0. 044 and Rw= 0. 058 for 3190 observed independent reflections. The distance between the two palladium atoms is 2. 5885(4) A. Each Pd ( I ) atom has a square-planar stereochemistry . There is a pronounced twist ad-out the Pd-Pd bond with the result that the dihedral angle between the coordination planes of two Pd atoms is 37. 6.     

The Molybdenum（0）Complex [Et4N]2[Mo2（CO）6（pys）2]（pys=Pyrindine—2—thiol

The title compound tetraethylammonium hexacarbonylbis(μ-pyridine-2-thiolato-S∶S) dimolybdenum [Et4N]2[Mo2(CO)6(pys)2] crystallizes in the monoclinic, space group, P21/c with a=13.217(2), b=21.648(2), c=27.193(6)(), β=82.52(2)°, V=7714.6()3, Z=8, Mr=840.77, Dc=1.45 g/cm3, μ=7.8 cm-1, R=0.038 and Rw=0.040 for 6082 reflections with I≥3σ(I). X-ray crystal structure study reveals that the asymmetric unit of the title compound is comprised of two independent formulations of the molecular formula. Each dianion has approximate C2 symmetry and the dimetallic Mo2S2 core adopts a "butterfly" conformation with a dihedral angle between the halves of 139.3(1)° for the first independent anion and 142.8(1)° for the second one. The two pyridine rings lie on the same side of the molecule in a cis arrangement and the Mo...Mo separations are 3.76(1) and 3.838(1)().     

两个新颖的联环十二烷衍生物的合成及结构表征

2-（2＇-Oxo-3＇-oximidocyclododecyl） cyclododecanone （1） and 2-（1＇-hydroxylcyclododecyl） cyclododecanone （2） were synthesized and characterized. The conformation analysis was carried out based on the NMR, molecular mechanics calculation and X-ray diffraction. The conformation of two cyclododecyl moieties of both 1 and 2 was found to be the [3333]-2-one or [3333] square conformation both in the crystal state and the solution. The dihedral angle between carbonyl and the oxime double bond of the ring B is 180°in the crystal of 1. The protons or hydroxyl group of carbon atoms to link the two cyclododecyl moieties of 1 and 2 constitute dihedral angles of 174°in the crystal, and 175°in the solution, and the C-C 6 bond between two cyclododecyl moieties can not freely rotate in the solid state and the solution. In addition, compound 2 was the first example of a-comer-anti-monosubstituted cyclododecanone. synthesis     

Synthesis,Bioactivity and Crystal Structure Analysis of Diisopropyl[（4-cyanopyrazol-3-ylamino）（2-hydroxyl-phenyl） methyl]phosphonate

The title compound,diisopropyl[(4-cyanopyrazol-3-ylamino)(2-hydroxylphenyl) -methyl] phosphonate was synthesized by the addition reaction of diisopropyl phosphite and N-(4-cyanopyrazole-3-yl) -2-hydroxylphenyl-imine. Its structure was characterized by IR,1H NMR,elemental analysis and single-crystal X-ray diffraction. The crystal belongs to the triclinic system,space group P1 with a = 9.1840(13) ,b = 9.2278(13),c = 12.1952(17) ,α = 93.846(2) ,β = 90.947(2) ,γ = 111.289(2) °,V = 959.9(3) 3,Dc = 1.309 g/cm3,Z = 2,μ(MoKa) = 0.173,F(000) = 400,the final R = 0.0414 and wR = 0.1196 for 2985 observed reflections(I > 2σ(I)) . The pyrazole and benzene moieties are approximately coplanar in each case. The dihedral angle between planes 1 and 2 is 82.99°. The crystal structure is stabilized by three intermolecular hydrogen bonds of O(1) -H(1) …O(2) ,N(2) -H(2) …N(3) and N(2) -H(2) …O(1) . Preliminary bioassay indicated that the title compound possessed antiviral activity to some extent.     

Synthesis, Crystal Structure, Physical Properties, and Application of a Series of Functional Dibenzo[d,f][1,3]dioxepine Derivatives

The twisted aromatics, functional dibenzo[d,f][1,3]dioxepine derivatives were synthesized in high yields from reactions of 5,5＇-dibromo-2,2＇-biphenol with corresponding ketal or ketone compounds under acid catalysis. The structures of these compounds were characterized by ^1H NMR, elemental analysis, UV-Vis absorption spectrum and X-ray diffraction analysis. The conformation of O--C--O bridged biphenyl derivatives with varied substitute groups on 6,6＇-position was studied by X-ray crystallography and force-field simulation. The result of calculations by UNIVERSAL 1.02 force field in Cerius2 package（4.6） indicates that dibenzo[d,f][1,3]dioxepine derivatives show twisted conformations and the twisted angle between the phenyl rings is about 40°, which is accordant with the result from crystal structure determination, though the obtained angles in the crystal of dibenzo[d,f][1,3]dioxepine derivatives with the varied substitute groups on 6,6＇-position are shown to be slightly shifted to 40° owing to intermolecular interactions in crystal stacking. DSC studies exhibit that the substitute groups on 6,6＇-position can induce a large variation of endothermic peaks ranging from 80 to 135 ℃. The conjugated polymers based on dibenzo[d,f][1,3]dioxepine derivatives, which have ultraviolet emitting with a quantum efficiency of 10%, were obtained by Yamamoto coupling.