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.

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 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.

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.

Hydrothermal Synthesis and Crystal Structure of a New Supramolecular Channel Framework Based on Cu Complexes and Polyoxovanadate:[Cu(I)(phen)_2]_5[HV_(15)O_(36)(Cl)]_(0.65)[H_3V_(16)O_(38)(Cl)]_(0.35)·2H_2O

A new compound [Cu（I）（phen）2]5[HV15O36（Cl）]0.65[H3V16O38（Cl）]0.35·2H2O 1 （phen = 1,10′-phenanthroline） has been prepared from the hydrothermal reaction of V2O5, CuCl, phen, H2C2O4·2H2O, THMAM （tris（hydroxymethyl）aminomethane） and H2O in the molar ratio of 3：1：1：0.5：2.5：1400. Compound 1 crystallizes in the space group P42212 of the tetragonal system with a = b = 21.5009（8）, c = 28.401（2） A, V= 13129.5（12） A^3 Z = 4, Dc = 1.800 g/cm^3, μ（MoKa） = 1.932 mm^-1, λ（MoKa） = 0.71073 A, F（000） = 7063.4, C120H81.20ClCu5N20O38.7V15.35, Mr = 3557.58, the final R = 0.0594 and wR= 0.1320 for 7761 observed reflections （I 〉 2σ（I））. Structure analysis shows that 1 exhibits a 3D channel framework formed by the supramolecular assembly of Cu complexes and polyoxovanadate clusters via intermolecular hydrogen bonding, and the channels contain Cu complexes. Other characterizations by elemental analysis, XPS, IR, XRD and thermal analysis are also described.

Synergistic activation of photoswitchable supramolecular assembly based on sulfonated crown ether and dithienylethene derivative

Conformational regulation among two or more distant sites is not only one of the main pathways to accomplish multiple tasks in complex biological systems but also represents a powerful strategy to obtain stimuli-responsive supramolecular nanoconstructs with tailored physicochemical performance.We herein report the fabrication of a photochromic supramolecular assembly,which can be synergistically activated by the conformational regulation with bis(4,8-disulfonato-1,5-naphtho)-32-crown-8 and then reversibly switched by the through-space communication between restricted stilbazolium salt and photochromic dithienylethene.This work demonstrates that the synergistic conformational modulation via intra-and intermolecular interactions can be developed as a generalizable approach to construct more advanced biomimetic nanomaterials.

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 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- .

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.

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.

Preparation and Crystal Structures of LaCl_3（12－crown－4）（MeOH）and［LaCl_3（phen）_2（H_2O）］·MeOH

The interaction of lanthanum(Ⅲ) chloride with 12-crown-4 in MeCN/MeOH mixed solvent produces an anhydrous complex,LaCl3(12-crown-4)(MeOH)(complex Ⅰ),C9H20O5LaCl3(Mr= 453.6),in which the La(Ⅲ) ion is 8-coordinated by three Cl anions,four oxygen atoms from a crown ligand and a methanol oxygen atom,the complex molecules were connected into a dimer by two O(MeOH)…Cl hydrogen bonds.Reaction of complex Ⅰ with phen(1,10-phenanthroline) gives the crystallization of[LaCl3 (phen)2(H2O)]·MeOH(complex Ⅱ),C25H22O2N4LaCl3(Mr= 655.8) in which the crown ligand is totally replaced by two phen molecules.Cell parameters for the two complexes are a= 9.389(3)[13.228 (5)],b=11.382(4)[10.767(3)],c=7.542(3)[18.520(6) ];α=94.32(3)[90.0],β=102.10(2)[102.01(3)],γ=91. 83(3)[90. 0]°with space group P1[P21/α];V=784.5(5)[2580(1)3,Z=2[4];μ(MoKα)=32.8[20. 2]cm-1;F (000)=444[1296];R=0.042[0.045];Rω=0.044[0.036] for 2398 [2345] observed reflections withⅠ>3σ(Ⅰ).The La(Ⅲ) ion in complex Ⅱ is 8-coordinated by three Cl anions,four N atoms of two phen molecules and one water molecule.The methanolmolecule forms a hydrogen bond with Cl(3) atom.

Crystal and Molecular Structure of BiCl3(15-Crown-5)

Single crystals of complex BiCl3(15-crown-5) were synthesized by gel method, and the structure was solved from X-ray diffraction data by direct and Fourier methods. The crystal is orthorhombic, space group is P212121 with unit cell parameters:a = 7. 677(4), 6=13. 254(6) and c= 15. 911(6) A , and 2=4. The final structural refinement converged with unweighted and weighted factors of 0. 053 and 0. 063 respectively for 1290 observed reflections. The structure consists of discrete BiCl3(15-crown-5) molecules in which bismuth atom is sandwiched between two essentially parallel planes, one of which contains five oxygen atoms and the other contains three chlorine atoms.

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.

Preparation and Crystal Structures of LaCl3（12－crown－4）（MeOH）and［LaCl3（phen）2（H2O）］·MeOH

The interaction of lanthanum(Ⅲ) chloride with 12-crown-4 in MeCN/MeOH mixed solvent produces an anhydrous complex,LaCl3(12-crown-4)(MeOH)(complex Ⅰ),C9H20O5LaCl3(Mr= 453.6),in which the La(Ⅲ) ion is 8-coordinated by three Cl anions,four oxygen atoms from a crown ligand and a methanol oxygen atom,the complex molecules were connected into a dimer by two O(MeOH)…Cl hydrogen bonds.Reaction of complex Ⅰ with phen(1,10-phenanthroline) gives the crystallization of[LaCl3 (phen)2(H2O)]·MeOH(complex Ⅱ),C25H22O2N4LaCl3(Mr= 655.8) in which the crown ligand is totally replaced by two phen molecules.Cell parameters for the two complexes are a= 9.389(3)[13.228 (5)],b=11.382(4)[10.767(3)],c=7.542(3)[18.520(6) ];α=94.32(3)[90.0],β=102.10(2)[102.01(3)],γ=91. 83(3)[90. 0]°with space group P1[P21/α];V=784.5(5)[2580(1)3,Z=2[4];μ(MoKα)=32.8[20. 2]cm-1;F (000)=444[1296];R=0.042[0.045];Rω=0.044[0.036] for 2398 [2345] observed reflections withⅠ】3σ(Ⅰ).The La(Ⅲ) ion in complex Ⅱ is 8-coordinated by three Cl anions,four N atoms of two phen molecules and one water molecule.The methanolmolecule forms a hydrogen bond with Cl(3) atom.

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 Characterization of Two [2]Catenanes Based on Phenylene-diacetylene Crown Ethers

Two charged donor-acceptor [2]catenanes were synthesized by the cyclization of the π-acceptor 1,1 ＇-[1, 4-phenylenebis-（methylene）]bis（4,4＇-bipyridinium）bis（hexafluorophosphate）（2） and bis（bromomethyl）benzene with the templates of the π-donor phenylene-diacetylene crown ethers la and lb in the yields of 31%, 35%, respectively. The mass spectra, 1H and 13C NMR spectra confirm that the phenylene-diacetylene crown ethers, with a nonaromatic ~r-system, successfully template the cyclization of CBPQT4＋. The X-ray crystallography analysis shows that the CBPQT4＋ ring encircles around the phenylene motif of the crown ethers, leaving the 1,3-butadiyne fragment out of the cavity of CBPQT4＋ ring. The mechanically interlocked structure of [2]catenanes was stabilized by the cooperative effects of π-stacking and hydrogen bonding interactions.

A Supermolecule Assembled and a-Dawson by Sodium Cation, Crown Ether Heteropolyanion

The supennolecular based on sodium molybdate（Ⅵ） and sulfate, dibenzo-18-crown-6 was synthesized in acetonitrile and characterized by elemental analysis, IR,^1H NMR, single crystal X-ray diffraction, indicating that it contains [S2M018062]^4＋ and [Na（DB18Cr）（H2O）]^＋, where each sodium ion is deviated from the plane defined by the oxygen atoms in the corresponding crown ether. The compound crystallizes in the monoclinic space group C2/c with a=3.29332（10） nm, b= 1.90917（6） nm, c=2.63132（7） nm, β= 121.6630（10）°, V=14081.8（7） nm^3, Z=8, T=293（2） K, and R1（wR2）=0.0177 （0.1525）. The compound exhibits a novel organic-inorganic structure, in which the crown ether-sodium complexes are coordinated to the terminal oxygen atoms of Mo18054 and the oxygen atoms of water molecule.