Nesting inclusion compounds. The X-ray structure of the 15-crown-5 sodium diphenylethyl diphenylmethyl cyanoacetonate complex

The action of sodium cyanide ongem -diphenyl-chloropropanone under phase transfer conditions in the presence of 15-crown-5 yields the title compound as a minor product. The crystal structure of this complex reveals that, in the solid state, the [15-crown-5-Na⁺] guest species is found within a loose cage of diphenylethyl diphenyl cyanoacetonate molecules with one open side of the cage blocked by an adjacent 15-crown-5 molecule. Colourless crystals of the compound belong to the monoclinic space groupP21/n witha = 12,255(2) Å,b = 13,005(1) Å,c = 23,433(2) Å, = 95,92(1) ° andD _c = 1.23 g cm^–3 forZ = 4.     

冠醚萃取苦味酸钪与配合物的晶体结构研究

研究了苯并15冠5(B15C5)和二苯并18冠6(DB18C6)萃取苦味酸钪的萃取平衡。在pH2～3,用斜率法确定了两种萃合物的组成,并由此计算了它们的表观萃取平衡常数。通过苯并15冠5苦味酸钪配合物的合成、表征及晶体的结构测定,讨论了萃取机理。     

The Syntheses and crystal structures of trans-dichlorobis (10-thiabenzo-15-crown-5)-palladium(Ⅱ)and trans-dichlorobis-(10-selenabenzo-15-crown-5)palladium(Ⅱ)

The preparation and X-ray crystal structures of the adducts of 10-thiabenzo-15-crown-5 and 10-selenabenzo-15-crown-5 with PdCl2 are reported. [PdCl2(C14H20O4S)2] (1): or-thorhombic, space group Pbca with cell dimensions of a=17.285(5), 6=8.354(3), c=21.689(4) A, K=3131.9 A3, Z=4;R=0.0330 for 2301 reflections with I > 3o(I), [PdCl2(C14H2oO4Se)2] (2): monoclinic, space group P21/n with cell dimensions of a=18.928(4), b=8.912(3), c=9.813(2) A, β=96.90(2)0, V=1643.4 A3, Z=2; R=0.0289 for 2617 reflections with I> 3σ(I), Both complexes are monomeric, square-planar palladiurn(Ⅱ) compounds with the Pd(Ⅱ) ion situating on a crystal-lographic inversion centre, and the crown ligands all adopt the axial coordination with the Pd-S bond of 2.3233(7) A and the Pd-Se bond of 2.4357(3) A. Their complexing characteristics are discussed in brief.     

冠醚萃取苦叶酸钪与配合物的晶体结构研究

研究了苯并１５冠５（Ｂ１５Ｃ５）和二苯并１８冠６（ＤＢ１８Ｃ６）萃取苦味酸钪的萃取平衡。在ｐＨ２～３，用斜率法确定了两种萃合物的组成，并由此计算了它们的表观萃取平衡常数。通过苯并１５冠５苦味酸钪配合物的合成、表征及晶体的结构测定，讨论了萃取机理。     

The X-ray structure of the trichlorocuprate of naphtho-15-crown-5 complexed potassium

The structure of the trichlorocuprate of naphtho-15-crown-5 complexed potassium has been determined by X-ray analysis. The crystal contains the complex cations [K(naphtho-15-crown-5)₂]⁺, the anion [Cu₂Cl₆]^2– and water molecules. The full composition of the compound in the solid state is represented by the formula [K(naphtho-15-crown-5)₂]₂[Cu₂Cl₆]·nH₂O), wheren3. The sandwich type cations are similar to those found previously for potassium complexes with benzo-15-crown-5. The coordination number of potassium is equal to 10; the coordination polyhedron is a 15-crown-5. The coordination number of potassium is equal to 10; the coordination polyhedron is a pentagonal antiprism. The water molecules are disordered and occupy six symmetrically independent positions with a probability of 0.5 in the crystal. The lack of close contacts between water molecules and the remaining components enabled the treatment of the complex as a clathrate. Supplementary Data relating to this article has been deposited with the British Library as Supplementary Publication No. 82154 (20 pages).     

f-Element/crown ether complexes: 21. Conformational changes in metal complexed versus hydrogen bonded benzo-15-crown-5 in the structure of [Y(OH2)3(NCMe)-(benzo-15-crown-5)][ClO4]3·benzo-15-crown-5·CH3CN

Crystalline [Y(OH₂)₃(NCMe)(benzo-15-crown-5)][ClO₄]₃·benzo-15-crown-5-CH₃CN can be obtained by slowly cooling a reaction mixture of Y(ClO₄)₃·n H₂O with benzo-15-crown-5 in a solution of acetonitrile and methanol (3 : 1) from 60°C to room temperature. The crystal structure of this complex has been determined at –150 and 20°C. The complex is triclinic,P . At –150°C the cell parameters area = 11.986(4),b = 12.071(7),c = 16.364(5) Å, = 93.56(3), = 98.68(3), = 109.68(4)°, vol = 2187 ų, andD _calc = 1.61 g cm^–3 forZ = 2 formula units. 3633 independently observed [F _o 5(F _o)] reflections were used in the final least-squares refinement leading to an agreement index ofR = 0.048. The Y(III) ion coordination geometry approximates a tricapped trigonal prism with three water molecules and three benzo-15-crown-5 oxygen atoms forming the prism, with the two remaining benzo-15-crown-5 oxygen atoms and the acetonitrile molecule completing the coordination as capping atoms. The three water molecules hydrogen bond a second crown ether molecule and two of the perchlorate anions. The two acetonitrile molecules have contacts with perchlorate oxygen atoms close enough for some weak interaction. One perchlorate is ordered, one is partially disordered as is the coordinated solvent molecule, and the third anion is totally disordered. The two unique crown ether molecules have distinctively different conformations.For Part 20, see reference [1].     

Crystal structures of the complexes of rare earth picrates with N, N, N'''', N''''-tetraphenyl-3, 6-dioxaoctanediamide

The complexes of rare earth picrate with N,N,N',N'-tetraphenyl-3,6-dioxaoctanediamide(TDD),Eu(picc(TDD)] 2CH3CN and [ Y(pic)3(TDD)],have been synthesized.The crystal structures reveal that TDD at is as n tetradentate ligand,forming a ring-like coordination structure with its oxygen atoms together with one oxygen atom of the bidentate pterate In the Eu(Ⅲ) complex,the europium ion with a larger ionic radius lies out of the ring,while in the Y(Ⅲ) complex,the yttrium ion with a smaller ionic radius enters the cavity of the ligand.The structures of the complexes are greatly affected by the ionic radii due to participation of the picrates in coordination.     

A PVC-based pentathia-15-crown-5 membrane potentiometric sensor for mercury(II)

Poly(vinyl chloride) (PVC)-based membrane of pentathia-15-crown-5 exhibits good potentiometric response for Hg²⁺ over a wide concentration range (2.51 × 10⁻⁵ to 1.00 × 10⁻¹ mol dm⁻³) with a slope of 32.1 mV per decade of Hg²⁺ concentration. The response time of the sensor is as fast as 20 s. The electrode has been used for a period of six weeks and exhibits fairly good discriminating ability towards Hg²⁺ in comparison to alkali, alkaline and some heavy metal ions. The electrode can be used in the pH range from 2.7 to 5.0.     

Crystal structures of the complexes of rare earth picrates with N, N, N′, N′-tetraphenyl-3, 6-dioxaoctanediamide

The complexes of rare earth picrate with N, N, N′, N′-tetraphenyl-3, 6-dioxaoctanediamide (TDD), [Eu(pic)₃(TDD)]-2CH₃CN and [Y(pic)₃(TDD)], have been synthesized. The crystal structures reveal that TDD acts as a tetradentate ligand, forming a ring-like coordination structure with its oxygen atoms together with one oxygen atom of the bidentate picrate. In the Eu (III) complex, the europium ion with a larger ionic radius lies out of the ring, while in the Y (III) complex, the yttrium ion with a smaller ionic radius enters the cavity of the ligand. The structures of the complexes are greatly affected by the ionic radii due to participation of the picrates in coordination. Project supported by the National Natural Science Foundation of China, the Doctoral Foundation of the State Education Commission of China, and the Climb Plan Foundation of the State Science and Technology Commission of China.     

芳香桥式双(苯并氮杂-15-冠-5)的合成及其对碱金属和重金属离子的选择键合

通过11,12-苯并-1,7,10,13-四氧杂-4-氮杂环十五烷-11-烯(苯并氮杂-15-冠-5)分别与间二苄溴, 间苯二甲酰氯和对苯二甲酰氯反应, 合成了N,N'-间二苄基双(苯并氮杂-15-冠-5) (1)、N,N'-间苯二甲酰基双(苯并氮杂-15-冠-5) (2)和N, N'-对苯二甲酰基双(苯并氮杂-15-冠-5) (3) 等三个芳香桥式双(苯并氮杂-15-冠-5)衍生物, 并解析了化合物3的晶体结构. 进而采用溶剂萃取的方法研究了它们与一价金属阳离子的键合行为. 结果表明, 双冠醚2对碱金属钠离子和重金属铊离子表现出较高的选择萃取能力, 而双冠醚1对重金属银离子表现出较高的选择萃取能力.     

Twelve-membered crown ethers: Crystal structures of benzo-12-crown-4 and naphtho-12-crown-4

The crystal structures of two 12-membered crown ethers, benzo-12-crown-4 (1) and naphtho-12-crown-4 (2), have been determined by X-ray analysis. Both structures are molecular. Compound1 is monoclonic,P2₁/b,a=8.466(3),b=8.019(3),c=33.590(10) Å, =90.99(3)^o. The unit cell contains two crystallographically independent molecules of1 with similar conformations. Compound2 is also monoclinic,P2₁/a,a=24.148(8),b=14.535(4),c=7.987(5) Å, =102.87(2)^o. Two independent molecules in the unit cell have significantly different conformations. Supplementary data relating to this publication have been deposited with the British Library as Supplementary Publication No. SUP 82145 (19 pages).     

The 1 : 1 complexes between benzo-18-crown-6, 18-crown-6 and aminosulfuric acid

The title compounds were prepared by treating a methanol solution of the corresponding crown ether with an aqueous solution of aminosulfuric acid.Crystals of [benzo-18-crown-6·H₂NSO₂OH] suitable for X-ray crystallography were obtained by recrystallization from methanol. The crystals are orthorhombic, space groupP2₁2₁2₁,a = 14.310(7),b = 12.516(4),c = 10.890(4) Å. Refinement led to a final conventionalR value of 0.051 for 909 reflections.Crystals of [18-crown-6·H₂NSO₂OH] suitable for X-ray crystallography were obtained by recrystallization from acetone. They are orthorhombic, space groupP2₁2₁2₁,a = 17.027(6),b = 14.866(5),c = 8.345(4) Å. The structure was solved by a heavy atom method and refined to an agreement value of 0.067.     

A novel covalent functionalisation of poly (styrene-alt-maleic anhydride) with 4-amino benzo-9-crown-3 ether

The grafting of 4-amino benzo-9-crown-3 ether to poly (styrene-alt-maleic anhydride) has been described. The covalent grafting of crown ether has led to a considerable increase in the solubility of polymer in organic solvents such as dimethyl sulphoxide, dimethylformamide and tetrahydrofuran. The highest solubility was attained in DMF and DMSO. The covalently bonded 4-benzo-9-crown-3 ether allowed the hosting of Li⁺. The covalently grafted crown ether to polymer was identified by infrared spectroscopy and thermogravimetric analysis methods.     

Indium-based liquid clathrates. II. Inclusion compounds derived from salts of the tetrachloroindate anion,InCl 4 − , and the crystal structure of [Li·15-c-5] [In(CH3)3Cl] (15-c-5=15-crown-5)

Indium(III) chloride reacts with 12-c-4 to give the 1:1 adduct [InCl₃·12-c-4]. This complex is a convenient In precursor to liquid clathrates. [InCl₃·12-c-4] reacts with LiCl to form [Li·12-c-4] [InCl₄]. When the reaction is carried out in the presence of an aromatic solvent such as toluene, a liquid inclusion complex forms readily. It has been determined that the C₆H₅CH₃:[Li·12-c-4] [InCl₄] ratio is 2. Alkylation of the 15-c-5 adduct of InCl₃ with methyllithium yields [Li·15-c-5] [In(CH₃)₃Cl]. The salt fails to form inclusion complexes with aromatic molecules. This compound has been characterized using single crystal X-ray diffraction. The molecule belongs to the monoclinic space groupP2₁/n, witha=7.515(2),b=18.952(6), andc=13.938(7) Å, =95.12(3)° andD _calc=1.43 g cm^–3 for Z=4. Least squares refinement based upon 2348 observed reflections led to a finalR=0.039. Supplementary Data relevant to this paper have been deposited with the British Library under number SUP82054 (20 pages).     

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

ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ［Ｌａ（ＮＯ_３）_３（１２－ｃｒｏｗｎ－４）－（Ｈ_２Ｏ）］（１２－ｃｒｏｗｎ－４）ＭａｏＪｉａｎｇ－Ｇａｏ；ＪｉｎＺｈｏｎｇ－Ｓｈｅｎｇ；ＹｕＦｅｎｇ－Ｌａｎ（ＬａｂｏｒａｔｏｒｙｏｆＲａｒｅＥａｒｔｈＣｈｅｍｉ?..     

苯并-15-冠-5取代的有机硅化合物的合成及其性能

我们提出了一条合成含有苯并-15-冠-5取代基的某些有机硅冠醚化合物的简易路线。通过Wittig反应合成的4'-乙烯基苯并-15-冠-5,经过双键上的硅氢加成反应,得到几种新型含有冠醚基团的有机硅烷或氯硅烷。后者可以进一步烷氧基化或者水解成冠醚取代的聚有机硅氧烷。此外,还测定了它们对碱金属离子的络合容量和作为相转移催化剂的能力。     

Reaction of trimethylaluminum with crown ethers. III. The synthesis and crystal structure of (12-crown-4)bis(trimethylaluminum)

The crown ether 12-crown-4 reacts with trimethylaluminum in toluene to form the complex [AlMe₃]₂[12-crown-4]. Attempts to utilize the remaining two oxygen atoms for coordination to AlMe₃ molecules were unsuccessful. The 21 complex crystallizes in the monoclinic space groupP2₁/n witha=11.342(7),b=12.941(4),c=6.973(6) Å, and =95.48(4)°. Refinement led to a finalR value of 0.047 for 925 observed reflections. The molecule resides on a crystallographic center of inversion, and as required by symmetry, the four oxygen atoms are planar. The Al–O bond is strong as revealed by the bond length of 1.977(3) Å. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82013 (9 pages).     

Crystal structure of inclusion compounds: The complexes of thecis-syn-cis and thecis-anti-cis isomers of dicyclohexano-18-crown-6 with 4-methylbenzenesulfamide

The crystal structure of two complexes of the isomerscis-syn-cis (isomer A) andcis-anti-cis (isomer B) of dicyclohexano-18-crown-6 with 4-methylbenzenesulfamide have been determined by X-ray single crystal diffraction methods. The two structures have been solved by direct methods and refined to agreement values of 0.067 and 0.038 for isomers A and B respectively. The first isomer forms an inclusion compound with a host/guest ratio of 1 : I; the second one of I:2. The amino groups of the guest molecules are connected by N-H...O hydrogen bonds with oxygen atoms of the polyether molecules. The methyl groups of 4-methylbenzenesulfamide do not form hydrogen bonds.[/p]The host-guest interactions in the molecular complexes, the reciprocal influence of the two molecules on their conformation and the intermolecular contacts between the molecules in the crystal are discussed.     

双臂式苯并-15-冠-5的合成及其对金属离子的选择键合

通过4,5-二溴甲基苯并-15-冠-5与2-萘酚和2-巯基苯并噻唑反应分别合成了两种新的双臂式苯并-15-冠-5(2和3),进而采用溶剂萃取的方法研究了它们与一些阳离子的键合行为.结果表明,冠醚2对碱金属钾离子和重金属铊离子表现出较高的选择性萃取能力,而冠醚3对重金属银离子表现出较高的选择性萃取能力.     

12-Membered crown ethers. Lipophilic derivatives of benzo- and naphtho-12-crown-4 and their membrane electrode properties. Crystal structures of benzo-12-crown-4 NaI and KI complexes

Lipophilic derivatives of benzo-12-crown-4 and naphtho-12-crown-4 have been synthesized. The behavior of the parent compounds and their derivatives in membrane ion-selective electrodes have been studied. Selectivity changes have been observed with the rise in lipophilicity. Crystal structures of the NaI and KI complexes of benzo-12-crown-4 (1 and2) have been determined by X-ray analysis. The alkali metal and iodide ions are in direct contact in2 but not in1. Compound1 [Na(benzo-12-crown-4)₂]·I is triclinic, witha=13.368(8),b=10.727(7),c=10.325(4) Å; =73.56(4),=77.73(4), =108.70(5)°;Z=2, space group is . Compound2 [K(benzo-12-crown-4)₂·I] is monoclinic, witha=15.807(8),b=12.043(4),c=15.601(6) Å,=117.74(3)°;Z=4, space groupC2/c. In both compounds the cations interact with all oxygen atoms of two crown ether molecules. Correlation of the crystal structures and behavior of the crown ethers in ion-selective membrane electrodes is discussed. Supplementary Data related to this article have been deposited with the British Library as Supplementary Publication No. 82185 (15 pages).