Crystal Structures of Ln（NO3）3（Ln=La,Yb）Complexes with 12—crown—4

ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｓｏｆＬｎ（ＮＯ_３）_３（Ｌｎ＝Ｌａ，Ｙｂ）Ｃｏｍｐｌｅｘｅｓｗｉｔｈ１２－ｃｒｏｗｎ－４ＭａｏＪｉａｎｇ－Ｇａｏ；ＪｉｎＺｈｏｎｇ－Ｓｈｅｎｇ；ＹｕＦｅｎｇ－Ｌａｎ（ＬａｂｏｒａｔｏｒｙｏｆＲａｒｅＥａｒｔｈＣｈｅｍ...     

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

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

f-Element/crown ether complexes. 27. The synthesis and crystal structure of [Ce(NO3)3 (OH2)(12-crown-4)] -12-crown-4

A unique cerium nitrate complex, [Ce(NO₃)₃(OH₂)(12-crown-4)]-12-crown-4, has been crystallized from the reaction of hydrated cerium nitrate and 12-crown-4. It crystallizes in the orthorhombic space group,Pnma, with (at –150°C)a = 22.901(5),b = 13.547(3),c = 8.422(1)Å, andD _x = 1.77 g cm^–3 forZ = 4 formula units. A finalR value of 0.048 was obtained utilizing 2059 unique observed [F _o 5(F _o)] reflections. The Ce atom resides on a crystallographic mirror plane and is 11-coordinate, coordinated to three bidentate nitrate groups, one water molecule and the four oxygens of one 12-crown-4 molecule. The water molecule hydrogen bonds a second 12-crown-4 unit. Both unique crown molecules and one of the nitrate anions are severely disordered.For part 26, see reference [1].     

Crystal Structure of [La(NCS)_3(18-crown-6)(DMF)]

ＣｒｙｓｔａｌＳｔｒｕｃｔｕｒｅｏｆ[Ｌａ（ＮＣＳ）_３（１８－ｃｒｏｗｎ－６）（ＤＭＦ）]ＭａｏＪｉａｎｇ－Ｇａｏ（ＦｕｊｉａｎＩｎｓｔｉｔｕｔｅｏｆＲｅｓｅａｒｃｈｏｎｔｈｅＳｔｒｕｃｔｕｒｅｏｆＭａｔｔｅｒ，ＡｃａｄｅｍｉａＳｉｎｉｃａ，Ｆｕｚｈ?..     

三水合硝酸钪18-冠-6配合物的合成及其晶体结构

报道了[Sc(NO3)3(OH2)3].(18-冠-6)的合成及其晶体结构.Sc(III)离子同三个双齿配体硝酸根与三个水分子氧配位,构成九配位的配合物.配位多面体是稍有扭曲的单帽四方反棱柱.配位水分子的六个氢原子分别与上下两层冠醚环上的氧原子生成氢键,形成多层夹心分子缔合物.     

CRYSTAL AND MOLECULAR STRUCTURE OF { CNa(15-crown-5)]_n [Cd(SCN)_3]}_n

<正> The complex [Na(15-crown-5)] [Cd(SCN)3] (15-crown-5 = C10H20 O5) crysializes in monoclinic space group P21/c with a=10. 219(2) ,b= 10. 575(2) ,c= 20. 572(2) A ,β=98. 45(1)°,V= 2198. 7A3,Mr=529. 89,Z = 4,Dx=1. 600g/cm3,F (000) -1052,μ= 15. 708cm-1. The structure was solved by direct methods with the final R=0. 064. Results of structure analysis indicate that the Na ion is bonded by 15-crown-5 to form a complex cation and the Cd(Ⅱ) is bonded by six SCN ion to form an anion chain with a distorted octahedral coordination.     

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

1INtrODUCTIONThecrownethercomPOundsandtheirderivativeshavecontinuouslyattractedconsiderableattentioneversincetheywerefirstreportedin1967illbecauseoftheirexcellentcapacitytoattachmetalatomstoformcomplexes.Nowadaystheyareappliedextensivelyinchemistry,biology,medicine,agriculture,metallurgyandmanyotherfields.Manypapersonsynthesesofnewcrownethers,theirstructuredeterminationandcharactersareoftenpublished.Inthestudiesthenitrifiedreactionofcrownetherisknownasasignificantwaybywhichfunctionalgroup…     

CRYSTAL STRUCTURE OF Ce(ClO_4)_3 COMPLEX WITH 3,3-R,R''''-16-C-5(R=CH_3;R''''=CH_3O(CH_2)_2OCH~-_2)

<正> The title compound C18H37O20NCeCl3, Mr = 834. 25, orthorhom-bic, P212121, a = 11.836(4), b = 13.899(6), c= 19. 401(6) A ; V=3192(2)A3; Z = 4; Dc=1. 74gcm-3, F (000) = 1684,μ= 17. 8cm-1 (MoKa). The final R = 0. 080, Rw = 0. 081. The Ce(Ⅲ) ion is coordinated to one O atom of one C1O4- ion, a CH3CN molecule, a water molecule and seven O atoms from a crown ether molecule. The other two C1O4- ions are not coordinated to the metal. The bond lengths of Ce-N(CH3CN), Ce -O(ClO4-), Ce -O(H2O) and Ce-O(crown) are 2. 61,2. 82,2. 53, and 2. 56A, respectively.     

Synthesis of a crystalline molecular complex of Y2+, [(18-crown-6)K][(C5H4SiMe3)3Y

The La(2+) complex [K(18-crown-6)(OEt(2))][Cp″(3)La] (1) [Cp″ = C(5)H(3)(SiMe(3))(2)-1,3], can be synthesized under N(2), but in the presence of KC(5)Me(5), 1 reduces N(2) to the (N═N)(2-) product [(C(5)Me(5))(2)(THF)La](2)(μ-η(2):η(2)-N(2)). This suggests a dichotomy in terms of ligands that optimize isolation of reduced dinitrogen complexes versus isolation of divalent complexes of the rare earths. To determine whether the first crystalline molecular Y(2+) complex could be isolated using this logic, Cp'(3)Y (2) (Cp' = C(5)H(4)SiMe(3)) was synthesized from YCl(3) and KCp' and reduced with KC(8) in the presence of 18-crown-6 in Et(2)O at -45 °C under argon. EPR evidence was consistent with Y(2+) and crystallization provided the first structurally characterizable molecular Y(2+) complex, dark-maroon-purple [(18-crown-6)K][Cp'(3)Y] (3).     

Reaction of early transition metal complexes with macrocycles. II. Synthesis and structure of TiCl3(H2O) · 18-crown-6, a compound with a unique bidentate bonding mode for the 18-crown-6 molecule

18-crown-6 reacts with TiCl₃ in CH₂Cl₂ to form a complex in which the crown ether functions as a tridentate ligand. Addition of moist hexane affords a molecular complex in which the crown ether functions as a bidentate ligand. A water molecule is bonded directly to the titanium atom and is further hydrogen bonded to three of the oxygen atoms of the crown. The deep blue crystals of the CH₂Cl₂ adduct belong to the monoclinic space groupP2₁/n witha=13.481(8),b=8.021(5),c=21.425(9) Å, =97.32(5)°, and _calc = 1.51 g cm^–3 forZ=4. Refinement led to a conventionalR value of 0.040 based on 873 observed reflections. The Ti–O bond distances for the crown oxygen atoms are 2.123(8) and 2.154(9) Å, while the oxygen atom of the water molecule is bonded at 2.072(8) Å. The octahedral coordination sphere of the titanium atom is completed by the three chlorine atoms at distances of 2.340(5), 2.352(4), and 2.373(4) Å. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82034 (10 pages).     

f-Element/crown ether complexes, 11. Preparation and structural characterization of [UO2(OH2)5] [ClO4]2·3(15-crown-5)·CH3CN and [UO2(OH2)5] [ClO4]2·2(18-crown-6)·2 CH3CN·H2O

The reaction of UO₂(ClO₄)·nH₂O with 15-crown-5 and 18-crown-6 in acetonitrile yielded the title complexes. [UO₂(OH₂)₅] [ClO₄]₂·3(15-crown-5)·CH₃CN crystallizes in the triclinic space groupPT with (at–150°C)a=8.288(6),b=12.874(7),c=24.678(7) Å, =82.62(4), =76.06(5), =81.06(5)°, andD _calc=1.67 g cm^–3 forZ=2 formula units. Least-squares refinement using 6248 independent observed reflections [F _o5(F _o)] led toR=0.111. [UO₂(OH₂)₅] [ClO₄]₂·2(18-crown-6)·2CH₃CN·H₂O is orthorhombicP2₁2₁2₁ with (at–150 °C)a=12.280(2),b=17.311(7),c=22.056(3) Å,D _calc=1.68 g cm^–3,Z=4, andR=0.032 (3777 observed reflections). In each complex the crown ether molecules are hydrogen bonded to the water molecules of the pentagonal bipyramidal [UO₂(OH₂)₅]²⁺ ions, each crown ether having exclusive use of two hydrogen atoms from one water molecule and one hydrogen from another water molecule. In the 15-crown-5 complex the remaining hydrogen bonding interaction is between one of the water molecules and one of the perchlorate anions. The solvent molecule has a close contact between the methyl group and a perchlorate anion suggesting a weak interaction. There are a total of three U-OH...OClO₃ hydrogen bonds to the two perchlorate anions in [UO₂(OH₂)₅] [ClO₄]₂·(18-crown-6)·2CH₃CN ·H₂O. The remaining coordinated water hydrogen bond is to the uncoordinated 2H₂O molecule, which in turn is hydrogen bonded to a perchlorate oxygen atom and an acetonitrile nitrogen atom. One solvent methyl group interacts with an anion, the other with one of the 18-crown-6 molecules. Unlike the 15-crown-5 structure, the hydrogen bonding in this complex results in a polymeric network with formula units joined by hydrogen bonds from one of the solvent molecules and the uncoordinated water molecule. Supplementary data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82051 (37 pages).For Part 10, see reference [1].     

Synthesis and Crystal Structure of a Cyano-bridged Bimetallic Complex[La(betaine)_2(H_2O)_6Fe(CN)_6]·2H_2O

1 INTRODUCTION In the last decade, cyano-bridged Prussian Blueanalogues[1] have been intensively studied from theviewpoint of application as functionalized molecule-based magnets[2], chemical sensor materials[3], fluo-rescent materials[4] and zeolitic-type materials[5, , 6]etc. In 1976, a series of cyano-bridged three-dimen-sional rare earth hexacyanometalates(IIILnM(CN)6?nH2O (M = Fe or Cr, n = 4 or 5) were crystallized andsubjected to single-crystal X-ray analysis[7]. …     

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].     

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).     

f-Element/crown ether complexes 2. The synthesis and crystal structure of Y(NO3)3(12-crown-4)

Y(NO₃)₃(12-crown-4) was prepared via reaction of the crown ether and Y(NO₃)₃·nH₂O in acetonitrile. Y(NO₃)₃(12-crown-4) crystallizes in the monoclinic space groupP2₁/c witha=12.084(5),b=8.524(4),c=15.150(6) Å, =91.62(3)⁰ andD _calc=1.92 g cm^–3 forZ=4. The structure was refined by least-squares to a final conventionalR value of 0.105 using 1249 independent observed reflections [I3(I)]. The title compound is isostructural with its Eu(III) analog. The yttrium ion is ten-coordinate, bonded to three bidentate nitrate groups and to the four oxygens of the crown ether. The coordination polyhedron is best described as a 4A, 6B-extended dodecahedron. The Y-O(nitrate) and Y-O(ether) separations average 2.44(5) and 2.46(4) Å, respectively.Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82040 (10 pages).For Part 1 see reference [6]     

稀土冠醚类配合物的研究 XX: 三价及二价稀土硫氰酸盐与辛二酰双(4'-苯并-15-冠-5)配合物的合成和性质

在乙腈和二氯甲烷混合溶液中合成了三价稀土元素(La, Nd, Eu, Dy, Er, Yb)硫氰酸盐与辛二酰双(4'-苯并-15-冠-5)的六个新配合物。并在氩气氛中, 以四氢呋喃为溶剂, 锂-萘为还原剂, 制得了二价铕硫氰酸盐与辛二酰双(4'-苯并-15-冠-5)的固体配合物。通过元素分析、红外光谱、差热热重分析、荧光光谱、穆斯堡尔谱、电子自旋共振谱、还原性实验等研究了双冠醚与稀土离子的配位作用, 并讨论了三价和二价稀土配合物在物理化学性质上的差别。     

Conformational analysis of 12-crown-3 and sodium ion selectivity of electrodes based on bis(12-crown-3) derivatives with malonate spacers

A conformational analysis was performed on two crown ethers (12-crown-3 and 12-crown-4) using a combination of semi-empirical and ab initio methods. The lowest conformations of 12-crown-3 and 12-crown-4 were found to have exodentate C_3v and C₂ structure, respectively. In the case of the sandwich-type complexation, the nucleophilic cavity of 12-crown-3 rather than that of 12-crown-4 seemed to be optimal for complexation with the Na⁺ ion. Four new bis(12-crown-3) derivatives (1–4) were examined as potential sodium ion-selective ionophores in poly(vinylchloride) (PVC) membrane electrodes. The ion-selective electrode (ISE) based on di(1,5,9-trioxacyclododecanylmethyl) 2-dodecyl-2-methylmalonate (1) had the highest selectivity for the sodium ion among the alkali and alkaline earths studied. The sodium ion selectivity of the ISE based on bis(12-crown-3) derivative 1 was superior to that of the ISE based on the bis(12-crown-4) analogue.     

CRYSTAL STRUCTURES OF La(NO_3)_3 COMPLEXES WITH BENZO-15-C-5 AND CYCLOHEXYL-15-C-5

<正> Complex La(NO3)3(Benzo-15-C-5) (C14H20LaN3O14, Mt= 593. 28) crystallizes in the orthorhombic,space group P212121 with a=8. 393(2),b= 16. 624(5), c = 17. 326(4) A ,V = 2417. 6(6) A3,Z = 4,DC= 1. 63gcm-3,F(000) = 1176, μ= 18. 7cm~1(MoKa). The final refinement converged with R = 0. 060 and Rw=0. 065 for 2223observed independent reflections. Complex La ( NO3 )3 ( Cyclohexyl- 15- C- 5 ) (C14H26LaN3O14,MT = 599. 34) is monoclinic,P21/n space group with a=9. 917(4),b= 13. 667(5),c=16. 763(5)A,β=104. 33(3),V = 2201(1)A3,Z=4,Dc=1.81gcm-3, F(000) = 1200,μ= 20. 4cm-1(MoKa).The final refinement converged with R=0. 048 and Rw=0. 036 for 1495 observed independent reflections. In the two complexes,the La (Ⅲ) ion is 11-coordinate and bonded to six oxygen atoms from three bidentate nitrate groups and five oxygen atoms from the crown ether. The average bond lengths of La -O (crown) and La -O(nitrate)are 2. 68 and 2. 61A for La(NO3)3(Benzo-15-C-5) ,re-snectively and 2. 71 and 2. 62 A for La(NO3)3(Cyclohexyl-15-C-5) re     

Synthesis,characterization, and crystal structures of two new divalent metal complexes of N,N'-bis(phosphonomethyl)-1,10-diaza-18-crown-6: a hydrogen-bonded 1D array and a 3D network with a large channel

Reaction of N,N'-bis(phosphonomethyl)-1,10-diaza-18-crown-6 (H(4)L) with copper(II) acetate in 1:1 ethanol/water mixed solvents afforded a new crystal-engineered supramolecular metal phosphonate, Cu(H(2)L) (complex 1). By reaction of the same ligand with cadmium(II) nitrate in a 2:1 (M/L) ratio in methanol, a cadmium(II) complex with a 3D network structure was isolated, Cd(2.75)(L)(H(2)O)(7) x 1.5NO(3) x 7H(2)O x MeOH (complex 2). The copper(II) complex crystallized in the monoclinic space group P2(1)/c, with a =10.125(4), b = 14.103(6), and c = 14.537(6) A, beta = 91.049(8) degrees, V = 2075.4(16) A(3), and Z = 2. The Cu(II) ions in complex 1 are 6-coordinated by two phosphonate oxygen atoms, two nitrogen, and two oxygen atoms from the crown ether ring. Their coordination geometry can be described as Jahn-Teller-distorted octahedral, with elongated Cu-O(crown) distances (2.634(4) and 2.671(4) A for Cu(1) and Cu(2), respectively). The other two crown oxygen atoms remain uncoordinated. Neighboring two Cu(H(2)L) units are further interlinked via a pair of strong hydrogen bonds between uncoordinated phosphonate oxygen atoms, resulting in a one-dimensional supramolecular array along the a axis. The cadmium(II) complex is tetragonal, P4(2)/n (No. 86) with a = 20.8150(9) and c = 18.5846(12) A, V = 8052.0(7) A(3), and Z = 8. Among four cadmium(II) atoms in an asymmetric unit, one is 8-coordinated by four chelating phosphonate groups, the second one is 8-coordinated by 6 coordination atoms from a crown ring and two oxygen atoms from two phosphonate groups, the third Cd(II) atom is octahedrally coordinated by three aqua ligands and three phosphonate oxygen atoms from three phosphonate groups, and the fourth one is 6-coordinated by four aqua ligands and two oxygen atoms from two phosphonate groups in a distorted octahedral geometry. These cadmium atoms are interconnected by bridging phosphonate tetrahedra in such a way as to form large channels along the c direction, in which the lattice water molecules, methanol solvent, and nitrate anions reside. The effect of extent of deprotonation of phosphonic acids on the type of complex formed is also discussed.     

Synthesis and reaction of the novel complex [AsPh4][OsCl5(H2O). X-ray structure analysis of [AsPh4][OsCl5(H2O)].2EtOH and [AsPh4][OsCl5(EtOH)].EtOH

The synthesis and characterization of the anionic mononuclear and homobinuclear osmium complexes [AsPh4][OsCl5L].xEtOH [L = H2O, x = 2 (9); L = EtOH, x = 1 (10a); L = py, x = 0 (10b)] and [AsPh4]2[Cl5Os(pyz)OsCl5] (12) (pyz = pyrazine) are described. Upon reduction in a chloride-containing medium, OsO4 (1) affords the osmium(IV) species [OsCl5(H2O)]- (2), which could be isolated by extraction with n-tributyl phosphate (TBP). Complex 9 is the first fully characterized chloroaquo complex of Os(IV). This complex is an effective starting material for the preparation of novel species, such as 10a, 10b, and 12. The X-ray structures of 9 and 10a were determined. Both compounds crystallize in the monoclinic space group P2(1)/n. 9: C28H34AsCl5O3Os, a = 10.910(4) A, b = 17.127(5) A, c = 17.555(7) A, beta = 103.77(2) degrees, V = 3186(2) A3, and Z = 4. 10a: C28H32AsCl5O2Os, a = 10.7762(2) A, b = 17.3939(1) A, c = 17.1477(3) A, beta = 103.645(1) degrees, V = 3123.45(8) A, and Z = 4. Complexes 9 and 10a crystallize with two and one molecule of EtOH and are bonded via hydrogen bridges to the H2O and EtOH ligand in 9 and 10a, respectively.