The polyiodide salts: Pyridinium pentaiodide;β-naphthylammonium pentaiodide; andN-methyl-γ-picolinium heptaiodide. Structures with channel inclusion features

The crystal structures of three polyiodode salts are reported (pyridinium pentaiodide, monoclinic,P2 ₁/m,a=9.221(5),b=12.918(5),c=6.026(4) Å, =103.60(7)^o,Z=2,R _F=0.087 for 1187 intensities; -naphthyl-ammonium pentaiodide, triclinic,173-1,a=10.390(5),b=9.502(5),c=4.462(3) Å, =99.19(7), =90.40(7),=108.49(8)^o,Z=2,R _F=0.059 for 1319 intensities;N-methyl--picolinium heptaiodide, monoclinic,C2/c,a=19.315(7),b=12.714(5),c=8.442(4) Å, =107.26(7)^o,Z=4,R _F=0.065 for 1336 intensities). All three structures can be described as having channel inclusion features; the cations are contained in channels in polyiodide frameworks based on different arrangements of I₂ molecules and I ₃ ^– anions. This structural type is the converse of the more widespread kind where polyiodide anions are contained in an organic matrix (e.g., cyclodextrin polyiodides). Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82016 (30 pages).Part X of Crystal Structures of Polyiodide Salts and Complexes. For Part IX, see F. H. Herbstein, G. M. Reisner, and W. Schwotzer,Acta Crystallogr. C, accepted for publication, 1984     

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].     

Crystal and molecular structure of a 1:1 complex of potassium perchlorotriphenylmethide and 18-crown-6 (1,4,7,10,13,16-hexaoxacyclooctadecane)

(C₆Cl₅)₃ C^– K⁺, C₁₂H₂₄O₆ is monoclinic, space groupP2₁ withZ=2,a=10.491(2),b=18.016(7),c=11.670(6) , =103.11(3)°,V=2148(1) ³, finalR=0.039 for 2339 observed reflections at room temperature. The overall shape of the perchlorotriphenyl free radical is given by the angles between the mean planes of each ring (around 70°). The K⁺ ion lies at the centre of the 18-membered macrocyclic ring. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. 82012 (19 pages).     

Coordination chemistry of alkali and alkaline earth cations. X-ray structural analysis of bis (benzo-15-crown-5) potassium nitrate monohydrate

The 1:2 charge separated KNO₃ complex with benzo-15-crown-5 (B15C5) has been crystallized from a 50% water-methanol solution. K(B15C5)₂NO₃·H₂O is monoclinic,P2₁/c,a=12.717(2),b=19.569(2),c=13.025(3) Å, =100.79(1)^o,Z=4,D _c =1.37 g·cm^–3. The X-ray structure was refined toR=0.052 for 3049 independent reflections withF ₀ ² 2.0(F ₀ ² ), collected with MoK radiation for a 2 -range of 4–44°. The K⁺ ion is coordinated tenfold in a crown sandwich through all five oxygen atoms of the macrocyclic ligand. Nitrate and water oxygens are not involved in the cation coordination sphere. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82031 (6 pages).     

Complexation with diol host compounds. Part 1. Structures of the 1:2 molecular complexes oftrans-9, 10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with acetophenone and with 3-methylcyclopentanone

The structures of the 1:2 molecular complexes of trans -9,10-dihydroxy-9,10-diphenyl-9,10-dihydroanthracene with acetophenone (1), (C₂₆H₂₀O₂·2 C₈H₈O) and with 3-methylcyclopentanone (2), (C₂₆H₂₀O₂·2C₆H₁₀O) have been determined by X-ray crystallography. The crystal data are as follows: Compound (1):P ,a =8.979(5) Å,b =9.316(3) Å,c = 11.12(1) Å, =94.40(6)°, = 106.53(6)°, = 109.92(5)°,V = 822.94 ų,Z = 1,R = 0.097 for 2549 unique reflections. Compound (2):P ,a = 8.958(7) Å,b =9.815(4) Å,c = 9.807(4) Å, = 96.88(3)°, = 109.21(8)°, = 103.33(7)°,V = 774.10 ų,Z = 1,R = 0.059 for 2494 unique reflections. The intermolecular arrangements in both structures are characterised by host-to-guest hydrogen bonding interactions. The thermal properties of compound (2) have been characterised by DTA and TGA thermograms.     

Aminosulfuric acid: An excellent guest for crown ether complexation. Crystal structure of the 1∶1∶1 molecular complex between aminosulfuric acid,water and 18,19-benzo-1, 16-diaza-4,7,10,13-tetraoxacycloeicosa-17,20-dione

The twenty-membered macrocycle, 18,19-benzo-1, 16-diaza-4,7,10,13-tetraoxacycloeicosa-17,20-dione, C₁₈H₂₆N₂O₆ (1), aminosulfuric acid and water form a stoichiometric 111 inclusion compound. The crystal structure of [1·NH ₃ ⁺ SO ₃ ^– ]·H₂O has been determined by X-ray crystallography. The crystal is monoclinic, space groupP2₁/c, a=7.967(1),b=13.447(3),c=20.779(4) Å, =90.20(2) Å;Z=4. The finalR-value is 0.0434 for 4638 unique reflections withI>2(I). The structure consists of the 11 molecular complexes between the crown host and aminosulfuric acid revealing hydrogen bonding with the ligand ether and carbonyl oxygen atoms. The complexes are united in the layer-like structure by NH...O host-guest and NH...O=CF _obs,F _calc, tables of anisotropic displacement parameters, and fractional atomic coordinates of hydrogen atoms.     

Dicyclohexylamides as ionophores for li-selective electrodes. Crystal structures of a triamide ligand and its complex with lithium ion

The influence of structure and lipophilicity of dicyclohexylamides on the lithium selectivity in membrane electrodes is discussed. The crystal structures of the triamide podand1 and its complex with LiBr1b has been determined by X-ray analysis. Crystal data for ligand1: C₄₈H₈₃O₆N₃, triclinic,P1,a=10.749(2),b=12.097(3),c=19.123(6)Å, =95.76(2),=80.06(2), =100.27(2)⁰,V=2403(1) ó,Z=2. Crystal data for the lithium complex1b: C₄₈H₈₃O₆N₃·LiBr·x C₂H₅OH, monoclinic,P2 ₁/c,a=21.297(6),b=16.316(8),c=19.450(4) Å,=110.87(2)⁰,V=6315(3) ų,Z=4. In the complex the ligand adopts a conformation in which oxygen binding sites surrounding the Li⁺ cation form a slightly distorted trigonal prism. Supplementary Data relevant to this article have been deposited with the British Library as Supplementary Publication No. 82177 (20 pages).     

X-Ray Diffraction Study of Piperidine Octamolybdate

Piperidine octamolybdate [C₅H₅NH₂]₄[Mo₈O₂₆]·4H₂O (I) has been synthesized and characterized by X-ray diffraction analysis. Crystals I are monoclinic, space group P2₁/n, a=12.892(3), b=9.283(2), c=19.184(4) , =92.50(3)°, V=2293.7(9) ³, Z=2,_calc = 2.317 g/cm³.     

Urea-water-anion Lattices Part 1. Crystal structures of (C2H5)4N+X−·(NH2)2CO·2 H2O (X=Cl,Br, CN), an isomorphous series of layer-type inclusion complexes

The title ternary complexes (1, X=Cl;2, X=Br;3, X=CN) have been prepared and characterized by X-ray crystallography. Crystal data: space groupP2₁/n,Z=4;1,a=7.505(2),b=14.556(4),c=14.453(3) Å, =98.13(2)^o, andR _F=0.088 for 1831 observed MoK data;2,a=7.483(1),b=14.643(6),c=14.443 Å, =98.25(2)^o, andR _F=0.113 for 923 data;3,a=7.490(2),b=14.646(5),c=14.594(5) Å, =98.85(5)^o, andR _F=0.082 for 915 data. In the isomorphous crystal structure of1 and2, ordered (C₂H₅)₄N⁺ cations are sandwiched between puckered layers matching the (020) family of planes, each being constructed from the cross-linking of planar zigzag chains of hydrogen-bonded urea molecules by the water molecules and halide ions. Compound3 has the same structure except that its cyanide group is disordered. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82066 (30 pages).Operated under contract DE-AC02-76CH00016 with the U.S. Department of Energy, Office of Basic Energy Science.     

Synthesis and Structure of Complexes Formed in the CuCl2–Cu–N-allylquinolinium Chloride System

The crystals of [C₉H₇N(C₃H₅)]₂Cu^IICl₄(IV) were obtained through ac electrochemical synthesis using CuCl₂· 2H₂O, N-allylquinolinium chloride, and copper electrodes in an ethanol-benzene medium. These crystals transformed with time into crystals of the [C₉H₇N(C₃H₅)][Cu^IICl₃(C₉H₇N)] complex (V). When tin(II) chloride was added to the initial reagents, the [C₉H₇N(C₃H₅)]Cu^I ₂Cl₃complex (VI) was obtained. The X-ray diffraction analysis (DARCh-1 autodiffractometer, MoK radiation, Zr filter) indicated that complexes IVand Vcrystallize in the triclinic system: space group P ; for IV, a= 12.817(4), b= 10.435(3), c= 9.606(3) Å, = 97.94(2)°, = 107.28(2)°, = 95.99(2)°, V= 1200.6(6) ų, Z= 2; for V, a= 16.992(5), b= 8.243(2), c= 7.345(3) Å, = 91.89(3)°, = 91.19(3)°, = 88.18(3)°, V= 1027.5(6) ų, Z= 2. Crystals VIare monoclinic, space group P2₁/n, a= 13.578(5), b= 15.079(4), c= 6.953(4) Å, = 105.08(4)°, V= 1370.6(10) ų, Z= 4. Structures IV–VIconsist of N-allylquinolinium cations and different anions: isolated [CuCl₄]^2–tetrahedrons (IV), [C₉H₇NCuCl₃]^–tetrahedrons (V) containing a quinoline molecule, and a polymer chain |[Cu^I ₄Cl₆]^2–} _n (VI) in which two independent metal atoms have trigonal-pyramidal and planar-trigonal environments. The C=C bond of the allyl group is not involved in cooordination with the Cu(I) atom.     

The crystal structure of Fe(SeO2OH)(SeO4)·H2O

Summary The crystal structure of the hydrothermally synthesized compound Fe(SeO₂OH) (SeO₄) · H₂O was determined by single crystal diffraction methods:a=8.355(2) Å,b=8.696(2) Å,c=9.255(2) Å, =93.72(1)°,V=670.95 ų;Z=4, space group P2₁/c,R=0.029,R _w=0.027 for 2430 independent reflections (sin /0.76 Å^–1). Isolated FeO₅(H₂O)-octahedra share five corners with [SeO₂OH] and [SeO₄] groups to form sheets parallel to (100). These sheets are interconnected via hydrogen bonds only.

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Die Kristallstruktur von Fe(SeO₂OH)(SeO₄)·H₂O

Zusammenfassung Die Kristallstruktur der hydrothermal dargestellten Verbindung Fe(SeO₂OH) (SeO₄)·H₂O wurde mittels Einkristallbeugungsmethoden bestimmt:a=8.355(2) Å,b=8.696(2) Å,c=9.255(2) Å, =93.72(1)°,V=670.95 ų;Z=4, Raumgruppe P2₁/c,R=0.029,R _w=0.027 für 2 430 unabhängige Reflexe (sin / 0.76 Å^–1). Isolierte FeO₅(H₂O)-Oktaeder teilen fünf Ecken mit [SeO₂OH]- und [SeO₄]-Gruppen, wobei sie Schichten parallel (100) bilden. Diese Schichten sind nur über Wasserstoffbrücken miteinander verbunden.

     

Crystal structure of an uncomplexed 25-crown-7 comprising one 2,6-pyridino and two 1,4-benzo condensations

Single crystal X-ray analysis of the uncomplexed crown macroring 1 is reported. Crystals are triclinic, , witha=10.809(1),b=10.945(1),c=10.256(1) Å, =107.85(1), =104.15(1), =87.27(1)°,D _c=1.318 g cm^–3,Z=2. Three torsion angles in the macrocycle take upgauche conformations in contrast to the usualanti conformation. The crystal structure is stabilized by intramolecular van der Waals forces and weak C–H...O and C–H...N hydrogen bond attractions. Stacking of pyridine rings is a noticeable packing feature in the crystal lattice. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82168 (6 pages).Macroring Uncharged Molecule Complexation. Part 20. For Part 19 of this series see Ref. [1].     

Crystal and molecular structure of 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane: Energy and structural relationships for this tetraazamacrocycle in its neutral and protonated forms

The X-ray crystal structure of 1,4,8,11-tetramethyl-1,4,8,11-tetraazacyclotetradecane has been determined. The neutral ligand crystallises in the triclinic space groupP with unit cell parametersa=8.467(4),b=10.057(5),c=10.637(5) Å, =67.68(3), =75.38(4), =76.34(4)°,V=800.75 ų andD _c=1.063 g cm^–3 forZ=2.R=0.047 for 2140 unique observed (I/(I)2.0) reflections (R _w=0.052). Two crystallographically independent molecules are observed. Both are centrosymmetric and adopt a mesodentate conformation. Molecule (1) is identified as the (R, S, S, R)-[trans-IV] isomer and molecule (2) as the (R, R, S, S)-[trans-III] isomer. Molecular mechanics calculations provide a basis for understanding the structural and energetic relationships between the neutral and protonated forms of this tetraazamacrocyclic ligand. Supplementary Data relating to this article have been deposited with the British Library at Boston Spa, Wetherby, West Yorkshire, U.K. as Supplementary Publication No. 82149 (13 pages).     

Hydrothermal Synthesis and Crystal Structure of a Europium(III) Coordination Polymer with 5-Sulfoisophthalate Trivalent Anions and Free 4,4′-Bipyridine Molecules

A novel europium(III) coordination polymer [Eu(Sip)(H₂O)₅]_n · nH₂O · 1.5n(Bipy) (I) (Sip is 5-sulfo-isophthalate trivalent anion and Bipy is 4,4-bipyridine) is hydrothermally synthesized and determined by the single crystal X-ray diffraction method. Polymer I crystallizes in the monoclinic system, space group C2/c with a=30.7515(6) , b=10.9577(2) , c=17.5545(4) , =112.040(1)°, V=5483.0(2) ³, Z=4, final R ₁=0.0253 and wR ₂=0.0606. In I, each Eu³⁺ ion is coordinated by four oxygen atoms from two carboxylate groups of two different Sip anions and five oxygen atoms from five coordinated water molecules to complete a deformed monocap square antiprism. Moreover, each Sip anion acts as a tetradentate ligand to connect two adjacent Eu³⁺ ions through its two chelating carboxylate groups, resulting in one-dimensional linear chains. In addition, fifteen different kinds of hydrogen-bonding interactions link the chains, lattice water molecules, and free Bipy molecules to engender a complicated hydrogen-bonding network.__________From Koordinatsionnaya Khimiya, Vol. 31, No. 5, 2005, pp. 391–396.Original English Text Copyright © 2005 by Hu Mao Lin, Cai Xiao Qing, Miao Qian, Xiao Hong Ping.This text was submitted by the authors in English.     

Coordination chemistry of alkali and alkaline earth cations: Crystal structure of rubidium (benzo-15-crown-5)2NO3·H2O

The complex Rb(B15C5)₂NO₃·H₂O is monoclinic,P2_1/c,a=12.695(3),b=19.471(3),c=12.991(2)Å, =99.60(2)^o,V=3166 ų,D _c =1.473 g/cm³ (163 K),D _c =1.434 g/cm³ (298 K),D _o =1.44 g/cm³ (298 K),T=163K,Z=4, MoK=0.71069 Å, 2(4^o–53^o), =16.43 cm^–1,F(000)=1424. FinalR for the 4588 observed reflections (F>3) is 0.062. All ten oxygens of the two benzo-crowns are shown to coordinate to the rubidium ion (Rb...O,2.92 to 3.07 Å) forming a charge-separated sandwich. The nearest nitrate oxygen is displaced 6.51 Å from the rubidium ion and is hydrogen bonded to a water molecule. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82028 (28 pages)     

Hydrogen bonding in 2-hydroxybenzoic, 2-hydroxythiobenzoic,and 2-hydroxydithiobenzoic acid. A structural and spectroscopic study

Summary X-ray structural data are reported for 2-hydroxythiobenzoic acid (T=200 K;P2₁/a;a=14.903(5) Å,b=5.203(3) Å,c=9.114(6) Å, =92.40(4)°;Z=4;R=0.049) and 2-hydroxydithiobenzoic acid (T=297 K;P2₁/a;a=14.416(3) Å,b=13.447(3) Å,c=3.947(1) Å, =90.96(2)°;Z=4;R=0.047). In 2-hydroxythiobenzoic acid, each two molecules form cyclic dimersvia S-H...O=C hydrogen bonds, analogous to the association pattern of 2-hydroxybenzoic acid. In 2-hydroxydithiobenzoic acid, the molecules are linked to chains by S-H...O(H)-C hydrogen bonds. Solid state IR, and solution IR and NMR spectroscopic data of 2-hydroxybenzoic acid, 2-hydroxythiobenzoic acid, and 2-hydroxydithiobenzoic acid are summarized. The main characteristics of the intramolecularly associated phenolic O-H groups of the three title compounds are for the solids, for solutions (CCl₄), and _OH=10.21, 10.53, 12.20 ppm for solutions (CCl₄:CDCl₃=5:1).Dedicated to Prof.O. Olaj on the occasion of his 60^th birthday     

Structure ofp-tetrakis-(4-nitrophenylazo)calix[4]-arene-4-picoline (1∶4) complex

The structure of thep-tetrakis-(4-nitrophenylazo)calix[4]arene-4-picoline (14) complex has been determined by X-ray crystallography. Crystals are monoclinic, space groupC2/c,a=24.9097) Å,b=8.425(6) Å,c=33.81(1) Å, =101.13(2)°,D _c =1.330 g/cm³,Z=4, finalR value =0.067. The cone conformation adopted by this azocalixarene is disturbed by the positions of the picoline molecules. Two of them are inside the macorocycle cavity and the two others are outside. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. Sup. 82190 (32 pages).     

Molecular inclusion in functionalized macrocycles. Part 12. Crystal and molecular structure of ap-(1,1,3,3)-tetramethylbutylcalix[8]arene octapodand

The title compound was obtained as colourless transparent prismatic crystals (from acetone/methanol 1:1), space groupPa=16.647(2),b=16.447(2),c=14.269(3) Å, =108.56(3), =105.63(3), =87.23(3)°,Z=1,D _calc=1.03 g cm^–3. Refinement was carried out using 2863 reflections, withI>(I). The molecule, which lies on a center of symmetry, possesses a roughly ellipsoidal shape with two sets of four phenolic nuclei following a helical arrangement. The polyether chains of two adjacent phenolic units partially fill the intramolecular cavity. No guest molecules are present. Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication SUP 82025 (22 pages).For part 11 see [1].     

Hydrogen-bonded urea-anion host lattices. Part 2. Crystal structures of inclusion compounds of urea with tetraalkylammonium bicarbonates

New inclusion complexes (C₂H₅)₄N⁺HCO ₃ ^– ·(NH₂)₂CO·2H₂O (1) and (n-C₄H₉)₄N⁺HCO ₃ ^– ·3(NH₂)₂CO (2) have been prepared and characterized by X-ray crystallography. Crystal data, MoK radiation:1, space groupP2₁/n,Z=8,a=9.356(1),b=29.156(4),c=12.161(1) Å, =90.03(1)°,R _F =0.062 for 2214 observed data;2, space groupP,Z=2,a=8.404(2),b=12.352(2),c=14.377(4) Å,a=88.20(2), =89.56(2), =71.68(1)°,R _F =0.052 for 3092 observed data. In both compounds the tetraalkylammonium ions are sandwiched between puckered layers, which are constructed from [((NH₂)₂CO)₂(HCO ₃ ^– )₂], ribbons, each composed of centrosymmetric hydrogen-bonded urea dimers and bicarbonate dimers, by lateral linkage through water molecules in1, and by direct cross-linkage of an alternate, parallel arrangement of the urea/bicarbonate and complementary urea ribbons in2. Supplementary Data relating to this article have been deposited with the British Library as Supplementary Publication No. SUP 82201 (40 pages).     

Polymorphism of Inclusion Complexes and Unsolvated Hosts. IV. Dimorphism of the Acetone Host–Guest Complex of Dianilinegossypol. Structures of the α- and β-Phase Complexes

Crystal structures of the - and -phase inclusion complexes of dianilinegossypol with acetone obtained at 20° and 30 °C, respectively, have been determined by X-ray structure analysis. Crystal data of the -phase complex are: C₄₂H₄₀O₆N₂2C₃H₆O, orthorhombic, space group Pccn, a = 29.501(9), b = 10.866(2), c = 13.756(3) Å, V = 4409(1) ų, Z = 4, D _x = 1.18 g cm^-3. The structure has been refined to a final R value of 0.117 for 1401 observed reflections. The host–guest ratio for the -phase complex is the same (1 : 2) and the crystals are monoclinic, space group C2/c, a = 28.352(6), b = 11.836(2), c = 13.196(1) Å, = 93.05(1)°, V = 4422(2) Å3, Z = 4, D _x =1.18 g cm^-3. The structure has been refined to a final R value of 0.077 for 1414 observed reflections.In both phases molecules of dianilinegossypol form hydrogen-bondedribbons by O(4)–-HO(3) H-bonds. Phases are determined by the same structural motif. In the -phase complex the cages are in the form of prisms but in the -phase clathrate they undergo a modification by shrinking in two directions and widening in one. Molecules of acetone are hydrogen bonded to the host molecules via aO(1)–-HO(G) bond and are accommodated in cavities for both complexes, i.e. both phases are cryptate-type inclusion complexes.Supplementary data relevant to this publicationhave been deposited with the British Library,No. SUP 82227 (24 pages).