Bibracchial Lariat Ethers(Ⅰ)——The Synthesis and Crystal Structure of the N,N'-bis(2-Methoxy-1-Naphthylmethyl)-4,13-Diaza-18-Crown-6 Sodium Iodide Complex

Diaza Crown ethers are versatile complexing reagents, their complexing abilities are dramatically modified by the electron donating atoms on substituents attached to the nitrogen if they can give a three-dimensional cavity as in cryptates. Hence the synthesis and characterization of bibracchial lariat ethers (BIBLES) have received much attention. In the preparation of new BIBLES, a complex Ⅱ was unexpectedly obtained.

Synthesis and Crystal Structure of Potassium Crown Ether Tetrathiosquarate

Slow diffusion of diethylether into a concentrated solution of K2C454.H20 and two equivalents of 18-crown-6 in pyridine affords dark orange crystals of bis（potassium{18-crown-6}）（3-cyclobutene-1,2-dithione-3,4-dithiolate） [K（C12H2406）]2（CnS4）. The crystal structure determination （monoclinic, P 2t/n, a = 12.2095（8） A, b = 11.3263（8） A, c = 14.0552（7） A, fl = 101.032（3）~, Z = 2） shows the presence of C4S42 - ions with almost undistorted D4h symmetry having C-C bond lengths of 1.442（10） A and 1.478（8） A and C-S bond lengths of 1.651（8） A and 1.664（7） A. Since the K＋ ions are shielded in a half-spherical way by the crown ether ligands, the crystal structures is built of centrosymmetric molecular entities [（18-crown-6）K（C4S4）K（18-crown-6）]. The K＋ ions have eight of coordination number, C4S42- acts as a chelating and bridging ligand towards two K＋ with K-S distances of 3.434（2） A and 3.380（2） A.

Synthesis,Crystal Structure and Thermal Decomposition of a New Energetic Potassium Salt of Bis(dinitromethyl)difurazanyl Ether

A new energetic organic potassium salt bis（dinitromethyl）difurazanyl ether potas- sium salt [K2（BDFE）] was synthesized, and structurally characterized by elemental analysis, IR spectra, t3C NMR and single-crystal X-ray diffraction. K2（BDFE） crystallizes in monoclinic system, space group C2/c with a = 17.342（3）, b = 12.6943（17）, c = 8.0972（11） A, β = 110.630（2）°, V = 1668.3（4） A3, Z = 4, Dc = 2.000 g/cm3, F（000） = 1000,μ= 0.675 mm-1, S = 1.058, the final R = 0.0499 and wR = 0.1452. The K ion is eight-coordinated with eight O atoms from one water molecule and four bis（dinitromethyl）difurazanyl ethers （BDFE）, forming a distorted dodecahedral structure. Thermal decomposition of the title complex was studied by using DSC and TG-DTG. There are primarily two exothermic decomposition processes between 200 and 370 ℃.

Synthesis and Crystal Structure of 3,3'-Dimethyl-dibenzo-18-crown-6

3,3′-Dimethyl-dibenzo-18-crown-6 was synthesized and characterized by elemental analysis, FT-IR, ^1H NMR, UV, MS spectra and X-ray single-crystal diffraction. It belongs to orthorhombic, space group Pna21 with a = 8.0790（18）, b = 16.780（4）, c = 15.222（3） .A, Z= 4, V= 2063.6（8） A3 Dc = 1.250 g/cm^3,μ = 0.090 mm^-1, F（000） = 832, R = 0.0474 and wR = 0.1103. According to structural analysis, the title compound possesses a boat-like configuration.

Synthesis and Crystal Structure of 13-Phenyl-1,10-dithia-4,7-dioxa-13-aza-15-Crown-5

Crystal structure of the title compound C 16 H 25 O 2NS 2 has been determined by X-ray diffraction method. Its crystallographic data were as follows: M r=327.51, triclinic, space group P1, a=8.864(3), b=10.127(4), c=10.390(3) , α=105.94(3), β=103.10(2), γ=90.96(3)°, V=870.3(7) 3, Z=2, D c=1.250g.cm -3 , μ(MoKα)=2.966cm -1 , F(000)=176, a total of 3275 reflections measured (2θ max =50°), 2246[I5σ(I)] used in the refinement, R=0.067, R w=0.082. The result shows that the distances of N(1)-C(2) and N(1)-C(3) are longer than that of N(1)-C(11), which indicates that the interaction of C Ar -N sp 2 is stronger than that of C sp 3 -N sp 2 . Oxygen, nitrogen and sulfur atoms of the ring in the same plane was deduced from the least\|squares planes and the dihedral angles.

Synthesis and Crystal Structure of Cu( Ⅱ ) Adduct with N-(4-Chlorophenyl)aza 15-Crown-5

The title compound C18 H25 NC4ClBr2Cu crystallizes in space group P 1 with a = 1.0105(2)nm b=1.0821(1) nm, c=1. 1007(2) nm, a=80. 00(1)°,β=80. 26(1)° γ=77. 83(1)°. Z=2, D = 1. 831 g/cm3, μ=62. 658 cm-1(Mok(?)). The final refinement converged to R=0. 031 for 2547 independent observed reflections. The complex molecule consists of two cationic moieties (HL)+ and an anion which appears as a bromide-bridged copper dimer (Cu2Br6)2-. This structural characterization seems to be rare in metal complexes with crown-ether.

Synthesis,Crystal Structure and Biological Activities of O-[(Z)-2-Methylbenzyl] 1-Phenyl-2-(1H-1,2,4-triazol-1-yl)ethanone Oxime

The crystal structure of the title compound （C18H18N4O, Mr = 306.36） has been determined by single-crystal X-ray diffraction. The crystal is of triclinic, space group P1 with α = 4.783（0）, b = 13.577（1）, c = 13.830（1） A, α = 63.581（2）, β = 88.326（2）, γ = 86.161（2）°, V= 802.5（1） A3, Z= 2, Dc = 1.268 g/cm^3, F（000） = 324, μ（MoKa） = 0.082 mm^-1, the final R = 0.0497 and wR = 0.1199 for 3094 observed reflections （I 〉 2σ（I））. The dihedral angles between the phenyl （C（1）-C（4）-（6）） and triazole, the phenyl （C（13）-C（15）-C（18）） and triazole, and the two phenyl rings are 7.9（1）, 69.9（1） and 67.8（1）°, respectively. Strong C-H…π interaction joins molecules into a chain along the c axis and contributes to the stability of the structure. Preliminary bioassay results show that the title compound possesses excellent and selective fungicidal activity against Colletotrichum gossypii but displays moderate to weak insecticidal activity against aphides.

Synthesis and Crystal Structure of One-dimensional Chain Complexes [K(18-C-6)]_2[M(mnt)_2](M=Zn,Hg)

The reactions of 18 crown 6 with each of K 2(M=Zn, Hg; mnt=1,2 dicyanoethene 1,2 dithiolate, C 2S 2(CN) 2- 2) were studied and novel complexes [K(18 C 6)] 2[Zn(mnt) 2](1) and [K(18 C 6)] 2[Hg(mnt) 2](2) were characterized by elemental analysis, IR spectrum and X ray diffraction analysis. Complex 1 displays a one dimensional chain of [K(18 C 6)] 2[Zn(mnt) 2] bridged by K O interactions between adjacent [K(18 C 6)] + units. Complex 2 is also a one dimensional chain of [K(18 C 6)] 2[Hg(mnt) 2] bridged by K...S weak interactions between adjacent [K(18 C 6)] + and [Hg(mnt) 2] 2- .

Two-dimensional Network Crown Ether Complex. Synthesis and Crystal Structure of 18-Crown-6 Complex: [K(18-C-6)]_2[Cd-(mnt)_2]

The novel complex [K(18-C-6)]_2 [Cd(mnt)_2] [18-C-6 = 18-crown-6, mnt =1,2-dicyanoethene-1,2-dithiolate, C_2S_2-(CN)_2^(2-)] was synthesized and characterized by elementalanalysis, IR spectrum and X-ray diffraction analysis. The complex displays two-dimensional networkstructure of [K(18-C-6)] complex segments and [Cd(mnt)_2] complex segment bridged by S-K-S, S-K-Nand N-K-N interactions between adjacent [K(18-C-6)] and [Cd(mnt)_2] units.

Synthesis and Crystal Structure of 15,16-Bis((4-nitrophenoxy)methyl)-2,3,5,6,8,9,11,12- octahydrobenzo[b][1,4,7,10,13]pentaoxacyclopentadecine

Double-armed crown ether 15,16-bis（（4-nitrophenoxy）methyl）-2,3,5,6,8,9,11,12-octahydrobenzo[b][1,4,7,10,13] pentaoxacyclopentadecine F.W. 570.54 was synthesized by dibromomethyl benzo-15-crown-5 with 4-nitrophenol in the presence of anhydrous K2CO3, characterized by spectroscopic techniques and confirmed by X-ray crystal structure analysis. The title compound crystallizes in monoclinic, space group P21/c with a = 12.840（4）, b = 9.425（3）, c = 22.447（7）, β = 98.128（7）° and Z = 4. The structure exhibits intermolecular hydrogen bonding of C-H···O type.

Studies on Heteromacrocyclic Polyether (X) Synthesis and Structural Characterization of 2, 3, 11, 12-Dibenzo-1, 4, 10, 13-tetraselena-7, 16-dioxacyclooctadeca-2, 11-diene

Dibenzo-1 , 4 , 10 , 13-tetraselena-7 , 16-dioxacyclo-octadeca-2 , 11-diene was synthesized by the condensation of poly (o-diselenobenzene) with bis (2-chloroethyl) ether in the presence of potassium borohydride. The molecular structure was examined by IR, MS and ￣1H NMR spectra, and confirmed by an X-ray diffraction study. The molecule in the crystal has a centrosymmetry and shows a chair conformation. The dihedral angle between the plane containing the four Se atoms and the benzene ring is 104. 1 (2)°. All geometrical parameters of the molecule are unexceptional. Crystal data : C_20H_24O_2Se_4, M_r= 612. 26, monoclinic, space group P2_1/c, a=8. 866(2) , b=5. 349(1). c=22. 315(3) A, β=96. 04(2)°, V=1052. 3 A￣3, Z=2,D_c=1.932 g/cm￣-3 , μ(MoKα) = 69. 15 cm￣-1, F(000) = 592, T= 297K, R= 0. 038for 1270 observed reflections and 154 refined parameters.

Crystal Structure of[La(NO_3)_3(12-crown-4)-(H_2O)](12-crown-4)

The crystal structure of crown ether-hydrogen bonded complex,[La(NO3)3 (12-crown-4) ( H2O)] (12-crown-4) has been determined by X-ray method. The title complex C16H34LaN3O18 (Mr=695. 5) crystallized in orthorhombic Pnma with a=23. 495(8), b=13. 603(5),c=8. 474(3); V=2706(1); Z=4 ; Dc=1. 71 g/cm3; F(000)=1408, μ=17. 0 cm-1 (MOKα). The final R=0. 052 and Rw= 0. 054(unit weight) for 1367 observed reflections. The La( Ⅲ) ion is 11-coordinated by three nitrale anions, four oxygen atoms from a crown ligand and one O atom of a water molecule. The other crown molecule is hydrogen bonded wilh the coordinated water molecule. The imposed mirror plane in the structure made both crown ligands and one of nitrate groups severely disordered.

Crystal Structures of Ln(NO_3)_3(Ln=La,Yb) Complexes with 12-crown-4

The synthesis and crystal structures of Ln(NO3)3(Ln=La,Yb) complexes with 12-crown-4 are reported. La (NO3 )3 (12-crown-4) (H2O)x(Ln=La,x=1; Ln=Yb, x=0), Mr=519. 2(535.3), space group P21/n(P21/c)with α =7. 612(2)(12. 116(3)), b=13. 932(6) (8. 544(3)),c= 16. 179(6) (15.241 (3));β=101.40 (2)( 91.82 (2))°; V=1682 (1) (1577(1)); Z=4 (4);μ(MoKα)=26.7(63.2) cm -1; F(000) =1024 (1036) ; R=0. 035 (0. 034) ; Rw= 0. 028 (0.036) for 1665 (1594) observed reflections with Ⅰ>3σ(Ⅰ). The La(Ⅲ) ion in La (NO3)3 (12-crown-4) (H2O) is 11-coordinated, being bonded to three bidentate nitrate ions , four oxygen atoms of the crown molecule and one oxygen atom of a water molecule. Yb(NO3)3 (12-crown-4) is a 10-coordinated complex, in which the metal ion bonds with three bidentate nitrate ions and four oxygen atoms of a crown ether.

Crystal Structures of Bis[aquachlorotriphenyltin(Ⅳ)] dihydrate·1,4,7,10,13,16-hexacyclooctadecane bis[aquachlorotriphenyltin(Ⅳ)]·1,4,7,10,13,16-hexacyclooct-adecane(3/1) and Bis[aquatrifluoroacetatotriphenyltin(Ⅳ)] dihydrate·1,4,7,10,13,16-hexa

In the crystal structures of the centrosymmetric isostructural co-crystals, bis[aqua- hlorotriphenyltin]dihydrate1,4,7,10,13,16-hexacyclooctadecane-bis[aquachlorotriphenyltin(Ⅳ)] 1,4,7,10,13,16-hexacyclooctadecane (3/1) 1 and bis[aquatrifluoroacetatotriphenyltin] dihydrate 1,4,7,10,13,16-hexacyclooctadecane-bis[aquatrifluoroacetatotriphenyltin(IV)]1,4,7,10,13,16- hexacyclooctadecane(3/1) 2, the crown ether interacts with the triphenyltin unit through both the coordinated and lattice water molecules in one molecular entity, but only through the coordinated water molecule in the other. The tin atoms are five-coordinate in trans-trigonal bipyramidal environments. Compound 1 is refined on 204 variables and 4665 I > 3s(I) reflections to R = 0.055, and compound 2 on 233 variables and 5721 I > 3s(I) reflections to R = 0.052. For crystal 1: C192H244Cl8O38Sn8, fw = 4392.99, trigonal, R3, a = 27.391(1), c = 23.007(1) ? V = 14948(1) ?, Z = 3, Dc = 1.464 g/cm3, F(000) = 6708 and m = 1.162 mm-1; and for 2: C208H244F24O54Sn8, fw = 5013.55, trigonal, R3, a = 28.775(1), c = 23.289(1) ? V = 16699(1) 3, Z = 3, Dc = 1.496 g/cm3, F(000) = 7620 and m = 0.978 mm-1.

Crystal Structure of Dimer Complex of 〔K (dndb)(H_2O)(NCS)〕_2

The title complex [K (dndb ) (H2O) (NCS ) ], (dndb = trans-dinitro-dibenzo-- 18 -- crown -- 6 -- ether ) crystallied in triclinic system, space group Pl wit h unit celldimensions a= 7. 844 (4), b= 11. 979(8), c= 14. 436(11) A; a= 75. 62(6), β=80. 15(5), γ= 71. 94(5)°, M.= 1131. 39, V= 1243(2) A3, Z= l, F(000) = 588, D.= 1. 511 g/cm3, μ= 10. 5 cm-l (MoKa). The final R= 0. 045 for 2740 observed reflections (I＞3σ). The title complex molecule is a dimer complex and the potassium(I) ionis nine--coordinated, being bonded to one NCS-- anion, one H2O molecule, six oxygenatoms of a crown ether ligand and an oxygen atom of a nitro of another crown ether ligand. The potassium(I) ion and the nine atoms bonded with it are all in two planeswhich are approximately vertical with each other. The trans--dinitro-- dibenzo-- 18 -- crown6 is a heptadentate ligand.

Synthesis, complexation properties and crystal structure of 4',5'-dibromo-oxylyl-17-crown-5 ether

4',5'-Dibromo-o-xylyl-17-crown-5 ether (2BrB17C5) was synthesized,starting from 1,2-dibromo-4,5-bis(bromomethyl)-benzene and tetraethylene glycol,and was characterized by 1H NMR,MS and elemental analysis.Pale yellow prismatic single crystal obtained from anhydrous ethanol was investigated by X-ray structural analysis.The complexation properties toward alkali metal ions were examined using the solvent extraction method and UV absorption spectroscopy.The crown ether was found to be conformationally deformed and oblate-like and is highly selective for lithium ion.

Synthesis and Crystal Structure of ［Na（DB18C6）（CH_3OH）］_2Mo_6O_（19）·（DB18C6）·（CH_3OH）

The preparation method of [Na ( DB18C6) (CH_3OH )]_2Mo_6O_(19)·(DB18C6)·(CH_3OH) , where DB18C6 is dibenzo-18-crown-6, is described. Thecrystal and molecular structure of the title complex has been determined crystallographically. The title complex crystallizes in the monoclinic system,space group P2_1/c ,a=18. 727(6) ,b=19. 555(6) , c=22. 827(7) ,β=112. 84(3)°, V=7704(4) ￣3 ,M_r = 2102. 9 , Z = 4 , F (000 ) = 4224 , μ= 1 . 028 mm ￣(-1), D_c = 1.813 g/cm￣3 . final R =0. 075 and R_w= 0. 078 based on 4463 observed reflections with F>6. 0σ(F) . The complex consists of [Mo_6O_(19)]￣(2-) ,[Na(DB18C6)]￣+ and CH_3OH, which are linked by long distance interaction through O-Na-O bond.

Synthesis and Crystal Structure of［Na（DB18C6）（H_2O）_2］_2Mo_6O_（19）·3DMF·2CH_3OH

The title complex [Na (DB_18C_6) (H_2O)_2]_2Mo_6O_19·3DMF · 2CH_3OH (Ⅰ) , a new type of crown hexamolybdate supermolecule, has been synthesized. Its crystal structure has been determined by X-ray diffraction analysis. The crystal C_49H_32 Mo_6N_2Na_2O_40 is tetragonal, space group P4/mbm, a= 17.108(2), c= 28. 285 (6) A ,V=8279(2) A￣ 3, Z=4 , M_r= 1960. 8 , D_x=1. 573 g/cm￣3 , P=9. 51cm￣(-1). F(000)=3936. The final agreement factors R=0. 058 and R_w= 0. 062 for 1777 independent reflections with F>4σ(F). In contrast to what we have reported about [Na(DB_18C_6)(CH_3OH)]_2Mo_6O_19(Ⅱ) where the whole complex was linked together, the cation [Na (DB_18C_6 ) (H_2O)_2]￣ + , that has crystallographic D_2h symmetry, combines with the anion with the symmetry O_h by electronic interaction.

SYNTHESIS OF DIAZA CROWN ETHER CHIRAL LIQUID CRYSTAL

A chiral liquid crystal crown ether containing diaza-18-crown-6 was synthesized with the help of CPK atomic model and in the meantime a nonchiral liquid crystal crown ether of alike structure was also synthesized for comparison, indicating that only the former was asymmetric. The present work represents the first attempt of the investigation in chiral liquid crystal crown ether, thus providing basis for further research into problems as such.