Macrocycle complexation chemistry. 38. Crystallographic and ultraviolet/visible characterization of nitrobenzo-15-crown-5, dinitrobenzo-15-crown-5, and dinitrodibenzo-18-crown-6·2CH3CN

The crystal structures of three nitrated benzocrown ethers have been determined. Nitrobenzo-15-crown-5 crystallizes in the orthorhombic space group,Pca2₁, witha = 15.367(2),b = 4.8499(8),c = 19.963(5)Å, andD _calc = 1.40 g cm^–3 forZ = 4. Dinitrobenzo-15-crown-5 crystallizes in the monoclinic space group,P2₁/n, witha = 11.716(2),b = 8.495(3),c = 17.441(5)Å, = 108.40(2)° andD _calc = 1.44 g cm^–3 forZ = 4.Dinitrodibenzo-18-crown-6·2CH₃CN ismonoclinic,P2₁/n,witha = 8.138(2),b = 20.435(9),c = 15.953(9)Å, = 100.55(4)° andD _calc = 1.36 g cm^–3 forZ = 4. The nitro substituents are in the plane of the benzo ring except in the sterically congested dinitrobenzo-15crown-5. The observed crown ether conformations are similar to their substituted analogs.For part 37, see reference [1].     

Neptunium(IV) Complex with Carbamide [Np(Urea)8]SiW12O40 · 2Urea · H2O: Synthesis,Crystal Structure,and Properties

The synthesis and crystal structure of [Np(Urea)₈]SiW₁₂O₄₀ · 2Urea · H₂O complex are reported. Crystallographic parameters: space groups C2/c, a = 18.972(5) Å, b = 18.891(5) Å, c = 16.654(4) Å, = 100.847(6)°, Z = 4, V = 5862(3) ų, (calcd) = 4.226 g/cm³. Thermal properties of this compound are studied; absorption spectra in the IR and visible regions are measured.     

Neptunium(V) Perrhenate Complex with 1,10-Phenanthroline [(NpO2)(ReO4)(Phen)(H2O)2]: Crystal Structure and Absorption Spectra

Neptunium(V) perrhenate complex [(NpO₂)(ReO₄)(Phen)(H₂O)₂] was synthesized with 1,10-phenanthroline as a ligand. Its composition and structure were determined by X-ray diffraction analysis. The coordination polyhedron of the Np atom is a pentagonal bipyramid. The nearest surrounding of the neptunoyl ion includes the oxygen atom of the ReO₄ anion, two nitrogen atoms of phenanthroline, and the oxygen atoms of two water molecules. The crystals of the compound are monoclinic. The main crystallographic parameters are the following: space group P2₁/c, unit cell parameters a = 7.288(1) Å, b = 10.513(2) Å, c = 20.936(4) Å, = 96.939(5)°, Z = 4, V = 1592.2(5) ų. Absorption spectra of the compound in visible and IR regions are reported.     

Crystal Structures of Cs+-Crown Ether Complexes Containing Polynuclear Mercury Iodide Anions

Reactions of CsI and HgI₂ with benzo-15-crown-5 (B15C5) and 15-crown-5 (15C5) in an ethanol-acetone mixture produced [Cs(B15C5)₂]₂[Hg₂I₆] (1) and {[Cs(15C5)]₂[Hg₂I₆]}_n (2), respectively. The structures of the two complexes are quite different. Molar ratios of Cs⁺ : crown ether are 1 : 2 in 1 and 1 : 1 in 2. Complex 1 consists of two Cs(B15C5) ₂ ⁺ cations and a Hg₂I ₆ ^2- anion. Cs⁺ lies between the two crown-5 ligands, resulting in a sandwich-type cation. Cationic Cs(B15C5) ₂ ⁺ and anionic Hg₂I ₆ ^2- are linked together by electrostatic interactions and the complex 1 is an ion pair compound. Complex 2 consists of infinite [Cs(15C5)]₂[Hg₂I₆] units. Each structural unit contains two Cs(15C5)⁺ cations and a Hg₂I ₆ ^2- anion. Cs⁺ is coordinated by five oxygen atoms of 15C5, three iodine atoms of Hg₂I ₆ ^2- , and an iodine atom of Hg₂I ₆ ^2- in an adjacent structural unit. The interactions between the Cs⁺ of Cs(15C5)⁺ and an I^– in Hg₂I ₆ ^2- from adjacent structural units polymerize the complex 2, resulting in a one-dimensional network structure. The anions of Hg₂I ₆ ^2- in both complexes are similar. The two mercury atoms are linked through two bridging iodine atoms and each mercury is also coordinated by two terminal iodines. Crystal data for 1: space group P2₁/c (No. 14), a = 12.253(4), b = 20.945(7), c = 16.110(6) Å, = 111.0(1)°, V = 3860 ų, Z = 4, R = 0.082 (R _w = 0.089). Crystal data for 2: space group P2₁/c (No. 14), a = 12.157(4), b = 8.546(4), c = 20.666(6) Å, = 91.54(3)°, V = 2146 ų, Z = 4, R = 0.034 (R _w = 0.048).     

Coordination chemistry of alkali and alkaline earth cations: Synthesis and crystal structure of potassium(benzo-15-crown-5)2 [3,5-dinitrobenzoate(3,5-dinitrobenzoic acid)2]

The interaction of K(35-Dnb) (35-Dnb=3,5-dinitrobenzoate) with benzo-15-crown-5 (B15C5) in ethanol yields a charge-separated sandwich structured complex [K(B15C5)₂]⁺[35-Dnb(35-DnbH)₂]^– even when equimolar amounts of reactants were used and no external 35-DnbH was added to the reaction mixture. The complex (KC₄₉H₅₁O₂₈N₆, FW=1211.1), is monoclinic,P2₁/c,a=11.063(2),b=10.680(1),c=46.548(8) Å, =91.629(2)⁰,Z=4,D ₀=1.485 g/cm³,D _c=1.468 g/cm³, CuK =1.5418 Å, =17.01 cm^–1, 2<130⁰,F(000)=2520,T=298 K. FinalR for the 6618 observed reflections was 0.071. In the sandwich moiety, the K⁺ is 10-coordinated through all the oxygens of the crown molecules (K⁺–O, 2.76–3.11 Å). The 35-Dnb anion lies 5.3 Å below the lower crown mean plane and is charge separated with respect to K⁺ (K⁺–O^–>7 Å) but undergoes strong hydrogen bonding (2.59 and 2.49 Å) through each carboxylate oxygen with the carboxylic protons of two separate 35-DnbH molecules. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82014 (52 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].     

Coordination chemistry of alkali and alkaline earth cations. Barium-crown encapsulation studies: The synthesis and crystal structure of barium(picrate)2(benzo-15-crown-5) monohydrate

The interaction of barium with benzo-15-crown-5 (B15C5) has been followed under the competitive effect of various chelating organic anions (L), nitrophenolates and nitrobenzoates, in ethanol and ethanol-water (9:1). The rather heavily hydrated BaL₂ salts yield novel 1:1 stoichiometric products in monohydrated or anhydrous states. Use of excess crown does not under any condition lead to the formation of 1:2 charge separated complexes, expected in view of the cavity and the cation sizes. The 1:1 Ba–B15C5 interaction is counteracted by L in accordance with its nucleophilicity, i.e., the pK _a value of its parent acid, HL. The complex Ba(picrate)₂(B15C5)·H₂O (BaC₂₆H₂₆N₆O₂₀, FW=879.0), is monoclinic,P2₁/c,a=11.43(1),b=16.31(3),c=17.38(2) Å, =92.265(3)°,Z=4,D _c=1.77 g/cm³,D ₀=1.73 g/cm³, MoK, =0.71069 Å, 2 (4.0–50°), =13.5 cm^–1,F(000)=1752,T=–32°C. FinalR for the 5926 reflections was 0.049. The structure reveals barium to be 10-coordinated through all the five crown oxygens (Ba–O, 2.800 to 3.002 Å), the two bidentate picrates (Ba–O, 2.642 and 2.666 Å; Ba–ONO, 2.825 and 2.994 Å), and the water molecule (2.711 Å) so that the cation constitutes a pseudo-sandwich of the crown on one side and the anionic species on the other. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82007 (50 pages). To obtain copies, see page ii of this issue.     

Complexation with hydroxy host compounds,part 5. Structures and thermal analyses of 1,2,3,4,5-pentaphenylcyclopenta-2,4-dien-1-ol and its inclusion compounds with water and dimethylsulphoxide

The crystal and molecular structures of the title host compound (I), C₃₅H₂₆O, and its inclusion complexes with water (II), C₃₅H₂₆O·H₂O and dimethylsulphoxide (III), C₃₅H₂₆O·C₂H₆OS are reported. (I) is monoclinicC2/c,a = 9.725(1),b = 20.031(3),c = 26.545(3) Å, = 90.60(1)⁰,V = 5170 ų,Z = 8; (II) is triclinic, ,a = 10.206(1),b = 10.324(2),c = 14.425(2) Å, = 101.68(1), = 89.92(2), = 116.34(1)⁰,V = 1327 ų,Z = 2; (III) is monoclinicP2₁/n,a = 17.832(5),b = 10.109(3),c = 17.901(5) Å, = 111.93(2)⁰,V = 2993 ų,Z =4. The structures were solved by direct methods and refined to final residuals of 0.045, 0.048, and 0.071, respectively. Thermal analysis of the complexes corroborates the crystallographic results.     

Neutral molecule/crown ether interactions 5. Comparison of the C−H acidic interactions of nitromethane and acetonitrile with 18-crown-6 and dibenzo-18-crown-6. Crystal structures of dibenzo-18-crown-6·2 CH3NO2 and dibenzo-18-crown-6·2 CH3CN

Complete structural characterization of dibenzo-18-crown-6·2 CH₃NO₂ and dibenzo-18-crown-6·2 CH₃CN have been carried out, including location and refinement of the methyl hydrogen atoms. Dibenzo-18-crown-6·2 CH₃NO₂ is monoclinic,P2₁/c, with (at –150°C)a=9.573(2),b=14.636(2),c=33.471(7) Å, =93.77(2)°, andD _calc=1.37 g cm^–3 forZ=8. Interactions between the solvent methyl groups and the crown ethers and other solvent nitro groups associate the 1 : 2 complexes into polymeric chains alongb. The acetonitrile adduct exists as discreet 1 : 2 complexes in the solid state with C–H...O interactions exlusively to the ether. This complex is triclinic,P 1, with (at –150°C)a=9.458(6),b=9.570(5),c=14.404(5) Å, =73.18(4), =79.85(5), =66.82(6)°, andD _calc=1.28 g cm^–3 forZ=2. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82070 (22 pages).For part 4, see reference [1].     

The synthesis and crystal structure of a copper-sulfur cluster [Cu4(S5)2(C5H5N)4]·S8

The cluster [Cu₄(S₅)₂(C₅H₅N)₄]·S₈ with cage structure has been obtained by reaction of copper powder with sulfur and K₂S _x in pyridine, and its structure was determined by X-ray crystallography. The crystal data for the title compound: triclinic, P (No. 2),Z = 2,a = 11.818(4) Å,b = 13.155(3) Å,c = 14.177(4) Å, = 93.79(2)°, = 96.68(2)°, = 115.76(2)°,V = 1954.52(1) ų. The structure was refined toR = 0.038R _w = 0.053) for 6444 data withI > 3.0(I).Dedicated to Professor Jiaxi Lu on the occasion of his 80th birthday.     

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 structure of the uncharged-molecule complex between a dinaphthopyridino-18-crown-6 host and acetonitrile (1 : 2)

Single crystal X-ray analysis of a 1 : 2 complex between the dinaphthopyridino-l8-crown-6 host (1) and acetonitrile is reported. Crystals of the complex are monoclinic,P2₁/c witha = 12.178(5),b = 8.186(1),c = 30.873(1) Å, = 96.86(1)°, andD _c = 1.25 g cm^–3 forZ = 4. The host molecule reveals an approximate mirror symmetry and exists in a so-called dentist's chair conformation. One of the acetonitrile guest molecules is involved in possible weak interactions to two oxygen atoms of the host macroring, while the other fills free lattice space only.     

Molecular structures of benzoylbenzo-12-crown-4 and diphenylacetylbenzo-12-crown-4 and possible reasons for different conformational states of their macrocycles

The molecular structures of (benzoyl)benzo-12-crown-4 (a=22.387,b=4.503,c=16.167 Å,d _calc=1.34 g cm^–3,Z=4, space groupP2₁ nc, DAR-UM, Cu-K,R=0.056) and (diphenylacetyl)benzo-12-crown-4 (a=8.866,b=23.337,c=10.737 Å;d _calc=1.25 g cm^–3,Z=4, space groupP2₁2₁2₁, DAR-UM, Cu-K, R=0.056) have been investigated. The differences in the conformations of the macrocycles and the degree of conjugation between the benzene ring orbitals and the lone pairs on the adjacent oxygen atoms in the macrocycle are discussed.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1906–1911, November, 1993.     

Stabilization of H2O ⁗ BF3 by hydrogen bonding to 18-crown-6

The decomposition of H₂O BF₃ in both the solid and solution states is rapid at room temperature, but 18-crown-6 H₂O BF₃,1, is stable to its melting point, 72°C.1 crystallizes in the monoclinic space groupC2/c witha = 27.273(9),b = 8.432(5),c = 22.936(9) Å, = 128.33(4)°, andD _c = 1.27 g cm^–3 forZ = 8. Least-squares refinement based on 1409 observed reflections led to a finalR = 0.083. The BF₃ is covalently bonded to the oxygen atom of the water molecule which in turn is hydrogen bonded to the 18-crown-6.     

Weak Interactions in Silver Complexes of 15-Crown-5

Abstract

The X-ray crystal structures of two closely related Ag(I) complexes of 15-crown-5 and benzo-15-crown-5 are reported. In the case of [Ag(15-crown-5)₂][SbF₆] 1, pointing one of its oxygen atoms away from the Ag⁺ cation enables one of the crown ligands to take part in an intermolecular C?H…O hydrogen bond. The analogous benzo-15-crown-5 species, [Ag(benzo-15-crown-5)₂][SbF₆] 2, is too rigid to attain the necessary conformation. Crystal data for 1: P2_1/c, a = 8.4481(3), b = 25.5813(9), c = 13.2773(4) Å, β = 101.354(2)°. Z = 4, unique data: 5187 R ₁ [F ² > 2σ(F ²)] 0.0259. Compound 2: P1, a = 8.6511 (15) Å, b =10.2322(18) Å, c = 19.291(3) Å, α = 103.704 (2)°, β = 101.274(2)°, γ = 95.952(2)°, Z = 2, unique data: 5803 R ₁ [F ²>2σ(F ²)] 0.0931.     

The crystal and molecular structure of a dinuclear copper(II) complex of a Robson-type macrocycle, [Cu2(C26H30N4O2)(H2O)2](BF4)2

Summary The crystal structure of the dinuclear complex [Cu₂(C₂₆H₃₀-N₄O₂)(H₂O)₂](BF₄)₂ was determined by x-ray crystallography. The crystals are triclinic, P¯1, witha = 10.945(5),b = 8.703(5),c = 8.495(5) Å, = 103.86(3)°, = 105.73(3)°, = 85.77(3)°, V = 756 ų D_c = 1.65 g cm^–3 for Z = 1. The copper(II) atoms are 5-coordinate and square-pyramidal. Selected bond distances are: Cu-N, 1.91 Å (mean); Cu-O(base) = 1.90(1) and 1.91(1) Å; Cu-O(apical) = 2.47(1) Å; There are O(water)-H ... F interionic hydrogen bonds in the structure. The Cu .. Cu distance is 2.847 Å.     

Palladium Clusters Pd4(SEt)4(OAc)4and Pd6(SEt)12: Structure and Properties

Palladium clusters Pd₄(SEt)₄(OAc)₄(I) and Pd₆(SEt)₁₂(II) were synthesized and studied. Their structure was determined by X-ray diffraction analysis. For I, a= 9.774(2) Å, b= 10.821(2) Å, c= 13.061(3) Å, = 92.88(3)°, V= 1379.6(5) ų, (calcd.) = 2.182 g/cm³, space group P2₁/n, Z= 4, N _ref= 1558, and R= 0.031; for II, a= 10.581(1) Å, b= 10.584(2) Å, c= 11.478(2) Å, = 101.62(1)°, = 104.95(1)°, = 106.74(1)°, V= 1135.2(4) ų, (calcd) = 2.007 g/cm³, space group P1, Z= 1, N _ref= 2828, and R= 0.022. In cluster I, four Pd atoms form a planar cycle. The neighboring palladium atoms are bound by two acetate or by two mercaptide bridges, the Pd···Pd distances being 3.036–3.195 Å. In cluster II, Pd atoms form a planar six-membered cycle with Pd···Pd distances of 3.083–3.127 Å. The neighboring palladium atoms are bound by two mercaptide bridges. The formation of analogous clusters in solution was confirmed by IR spectroscopy.     

Indium-based liquid clathrates. I. The preparation of the first indium liquid inclusion compound and crystal structure of its parent complex, [K · 18-Crown-6]2[InClI2(CH3)][InClI(CH3)2]

The synthesis of the first liquid clathrate derived from an indium precursor is described. The aromatic/anion ratio of the inclusion complex prepared using benzene is 12.4. The use of toluene results in the inclusion of 10.3 guest toluene molecules/anion. The crystal structure of the parent complex, [K·18-Crown-6]₂[InClI₂(CH₃)][InClI(CH₃)₂] was carried out. The compound belongs to the monoclinic space groupP2₁/c, witha=19.508(9),b=8.503(5), andc=29.437(9) Å, =96.55(3)°, andD _calc=1.83 g cm^–3 forZ=4. Least-squares refinement based on 3449 observed reflections led to a finalR=0.099. The structure displays two different environments for the two K⁺ cations in the asymmetric unit. One adopts the near-planar [K·18-crown-6]⁺ configuration while the other K⁺ resides 0.81 Å above the second 18-crown-6 plane. The latter K⁺ is apparently pulled out of the crown by a strong interaction with a Cl^– ion. Supplementary Data related to this article are deposited with the British Library as Supplementary Publication No. SUP 82046 (25 pages).     

Synthesis and Structure of Tin(II) Hexafluorozirconate

The crystal structure of SnZrF₆ is determined. The compound is synthesized by slow crystallization from a melted mixture of SnF₂ and ZrF₄ (2 : 1). The crystals are monoclinic: a = 6.6119(5), b = 5.2503(5), c = 6.9929(6) Å, = 114.239(4)°, space group P2/n, Z = 2. The structure is layered. The layers are formed from the chains of edge-sharing, eight-vertex zirconium polyhedra and Sn²⁺ cations. The Zr–F and Sn–F bond lengths in the layer vary from 2.309(1) to 2.269(1) Å and from 2.186(1) to 2.361(1) Å, respectively. The layers are linked by intermolecular Sn–F bonds with lengths of 2.868(1) and 2.871(1) Å.     

Synthesis,Crystal Structure,and Absorption Spectra of Neptunium(V) Di(acetamido) Nitrate (NpO2)(NO3)(CH3CONH2)2

The crystal structure of (NpO₂)(NO₃)(CH₃CONH₂)₂ was determined. The crystallographic data were are follows: a = 5.766(3) Å, b = 13.154(5) Å, c = 14.027(6) Å, V = 1064.0(8) ų, space group Pnma, Z = 4, _calcd = 2.804 g/cm³, R = 0.046, R _w = 0.102. The coordination polyhedron of Np is a pentagonal bipyramid whose equatorial positions are occupied by the oxygen atoms of the neighboring NpO₂ group, acetamide molecules, and of the nitrate ion. The IR and electronic absorption spectra of the compound were measured.