Crown ether complexes exhibiting unusual 1:2 macrocycle salt ratios: X-ray crystal structures of cyclohexano-15-crown-5•2LiOPh, cyclohexano-15-crown-5•2NaOPh, and 15-crown-5•2NaOPh

1991 ◽  
Vol 69 (4) ◽  
pp. 687-695 ◽  
Author(s):  
Kimberly A. Watson ◽  
Suzanne Fortier ◽  
Michael P. Murchie ◽  
John W. Bovenkamp
Keyword(s):  
Crown Ether ◽  
Alkali Metal ◽  
Crystal Structures ◽  
Direct Methods ◽  
The Other ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
Host Guest Complex ◽  
Crown Ether Complexes

The crystal structures of three crown ether complexes (cyclohexano-15•crown-5•2LiOPh (1): Li2O7C26H36, Mr = 474.45, λ(CuKα)filt. = 1.5418 Å; cyclohexano-15-crown-5•2NaOPh (2): Na2O7C26H36, Mr = 504.54, λ(CuKα)filt. = 1.5418 Å; and 15-crown-5•2NaOPh (3): Na2O7C22H30, Mr = 452.46, λ(CuKα)mono. = 1.5418 Å) have been determined by X-ray diffraction at room temperature (T = 298 K). Complex 1 crystallizes in space group P21/n with a = 15.032(5), b = 13.332(2), c = 13.533(3) Å, β = 106.28(2)°, V = 2603.2 Å3, and Z = 4. Complex 2 crystallizes in space group P21/n with a = 15.94(1), b = 12.194(7), c = 14.068(7) Å, β = 102.84(5)°, V = 2666.3 Å3, and Z = 4. Complex 3 crystallizes in space group P21/c with a = 12.451(3), b = 17.263(3), c = 12.659(6) Å, β = 115.74(3)°, V = 2450.8 Å3, and Z = 4. The three structures were solved by direct methods and refined by full-matrix least-squares calculations to residuals, R, of 0.080, 0.069, and 0.081 for complexes 1, 2, and 3, respectively. In each structure the macrocycle forms a 1:2 host–guest complex with the alkali metal. Each structure exhibits a dimer of the general form (MAC•2MOPh)2 where M = Li+ and Na+ for structures 1 and 2, respectively, and MAC = cyclohexano-15-crown-5, while M = Na+ and MAC = 15-crown-5 for structure 3. In each case the two metals of the monomeric unit have different crystallographic and chemical environments. In structures 1 and 3 one alkali metal is coordinated to all five oxygens of the macrocycle and to one of the phenoxide oxygens, while the other alkali metal is coordinated to only one oxygen of the macrocycle and to three phenoxide oxygens. In structure 2, one alkali metal is coordinated to only four of the five oxygens of the macrocycle and to two of the phenoxide oxygens, while the other alkali metal is coordinated to only one oxygen of the macrocycle and to three phenoxide oxygens (as in 1 and 3). Key words: crown ether, host–guest complexes, X-ray crystallography.

The crystal structures of the 1:2 host:guest complexes of dicyclohexano-18-crown-6 (isomers A and B) with sodium and potassium phenoxide

1986 ◽  
Vol 64 (4) ◽  
pp. 816-823 ◽  
Author(s):  
Marie E. Fraser ◽  
Suzanne Fortier ◽  
André Rodrigue ◽  
John W. Bovenkamp
Keyword(s):  
Crown Ether ◽  
Crystal Structures ◽  
Metal Cation ◽  
Direct Methods ◽  
The Other ◽  
Full Matrix ◽  
Space Group ◽  
Elliptical Cavity ◽  
Cation Coordination ◽  
Sodium And Potassium

The crystal structures of the 1:2 host:guest complexes of dicyclohexano-18-crown-6 (isomer B) with potassium phenoxide and dicyclohexano-18-crown-6 (isomer A) with sodium phenoxide have been determined. The potassium phenoxide complex crystallizes in space group [Formula: see text] with a = 10.023(2), b = 11.238(2), c = 7.546(2) Å, α = 95.73(2), β = 103.04(2), γ = 92.03(2)°, and Z = 1. The sodium phenoxide complex crystallizes in space group P21/n with a = 19.185(12), b = 13.266(5), c = 13.038(5) Å, β = 96.55(4)°, and Z = 4. Both structures were solved by direct methods and refined by full matrix least-squares calculations to a residual, R, of 0.035. The host conformation as well as the metal cation coordination differ considerably in the two structures. In the potassium phenoxide complex, the two cations are related by symmetry and have, consequently, the same chemical environment. Each potassium is located approximately halfway between the plane formed by the crown ether oxygens and the phenoxide anions and is coordinated to four of the crown oxygens and to two phenoxide oxygens. The oxygens of the crown are found to outline an elliptical cavity and to lie approximately in a plane. In the sodium phenoxide complex, the two sodiums have different crystallographic and chemical environments. One sodium is coordinated to the six hexaether oxygens, with distances ranging from 2.36to2.84 Å, and to one of the phenoxide oxygens. The other sodium is coordinated to only one of the crown oxygens and to three of the phenoxide oxygens. The hexaether adopts a highly irregular conformation.

Complexes of 15-crown-5 and cyclohexano-15-crown-5 with lithium, sodium, and potassium phenoxide having macrocycle: salt ratios of 1:1 and 1:2. The crystal structures of two polymorphs of 15-crown-5•2LiOPh

1988 ◽  
Vol 66 (10) ◽  
pp. 2515-2523 ◽  
Author(s):  
Michael P. Murchie ◽  
John W. Bovenkamp ◽  
André Rodrigue ◽  
Kimberley A. Watson ◽  
Suzanne Fortier
Keyword(s):  
Crystal Structures ◽  
Direct Methods ◽  
The Other ◽  
X Ray Diffraction ◽  
Full Matrix ◽  
Space Group ◽  
X Ray ◽  
Diffraction Structure ◽  
Structure Determinations ◽  
Sodium And Potassium

The syntheses, in ethereal solvents, of the complexes of 15-crown-5 and cyclohexano-15-crown-5 with lithium, sodium, and potassium phenoxide are described. The two macrocycles form complexes with lithium and sodium phenoxide with host:guest ratios of 1:2. Potassium phenoxide, however, was complexed by the two macrocycles to give products with macrocycle:salt ratios of 1:1. Crystals of 15-crown-5•2LiOPh were obtained for X-ray diffraction structure determinations. In fact, the crystal structures of two co-crystallizing polymorphs of this complex (1a and 1b) have been determined. Polymorph 1a crystallizes in space group [Formula: see text] with a = 11.386(4), b = 11.901(4), c = 10.654(4) Å, α = 106.53(3), β = 112.60(3), γ = 106.52(3)°, and Z = 2. Polymorph 1b crystallizes in space group P21/n with a = 15.355(4), b = 11.642(2), c = 13.595(6) Å, β = 104.56(3)°, and Z = 4. Both structures were solved by direct methods, and refined by full-matrix least-squares calculations to residuals, R, of 0.053 and 0.055 for polymorphs 1a and 1b, respectively. The structures of the two polymorphs differ only in the orientation of the phenoxides. The structures show a dimer, (15-crown-5•2LiOPh)2, which consists of an aggregate of four lithium phenoxide molecules complexed by two 15-crown-5 macrocycles. The two lithiums of each monomeric unit of this dimer have different crystallographic and chemical environments. One lithium is coordinated to all five oxygens of the macrocycle and to one of the phenoxide oxygens while the other lithium is coordinated to only one oxygen of the macrocycle and to three phenoxide oxygens.

Unexpected Structural Diversity in Alkali Metal Azide-Crown Ether Complexes: Syntheses, X-ray Structures, and Quantum-Chemical Calculations

2006 ◽  
Vol 12 (9) ◽  
pp. 2620-2629 ◽  
Author(s):  
Michael D. Brown ◽  
John M. Dyke ◽  
Francesco Ferrante ◽  
William Levason ◽  
J. Steven Ogden ◽  
...  
Keyword(s):  
Crown Ether ◽  
Alkali Metal ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
Structural Diversity ◽  
X Ray ◽  
Metal Azide ◽  
Crown Ether Complexes

Die Kristallstrukturen von Tetraphenylphosphonium- octahalogenodiarsenat( III) und -diantimonat(III) mit Acetonitril, (PPh4)2[E2X8] · CH3CN (E = As, Sb; X = CI, Br)/The Crystal Structures of Tetraphenylphosphonium Octahalogenodiarsenate (III) and Diantimonate (III) with Acetonitrile, (PPh4)2[E2X8]·CH3CN(E=As, Sb; X=Cl, Br)

1999 ◽  
Vol 54 (2) ◽  
pp. 288-290 ◽  
Author(s):  
Wolfgang Czado ◽  
Susanne Rabe ◽  
Ulrich Müller
Keyword(s):  
Crystal Structure ◽  
Crystal Structures ◽  
The Other ◽  
Space Group ◽  
X Ray ◽  
Structure Determinations ◽  
Cl Atoms

(PPh4)2[As2Cl8] · CH3CN was obtained from PPh4Cl and S2Cl2 with As or As4S4 or AsCl3 in acetonitrile. PPh4Cl, S2Cl2 and Sb2S3 yielded (PPh4)[Sb2Cl8] CH3CN. PPh4Br and AsBr3 gave (PPh4)2[Sb2Br8]-CH3CN. AsCl2OPh (from AsCl3 and NaOPh) reacted with Ph4Br in acetonitrile in the presence of Na2Se, selenium, and HCl, affording (PPh4)2[As2Br4,2Cl3,8] · CH3CN. According to their X-ray crystal structure determinations, all products are isotypic (space group C2/c, Z=4). The centrosymmetric anions consist of two ψ octahedra sharing an edge. In the [As2Br4,2Cl3,8]2- ion the bridging positions are taken solely by bromine atoms, whereas Br and Cl atoms occupy the other halogen positions randomly.

scholarly journals Kristallstrukturen der Tetrachloroniccolate (PPh4)2[NiCl4] und [Na-15-Krone-5]2[NiCl4] / Crystal Structures of the Tetrachloroniccolates (PPh4)2[NiCl4] and [Na- 15-Crown-5]2[NiCl4]

1990 ◽  
Vol 45 (7) ◽  
pp. 995-999 ◽  
Author(s):  
Karin Ruhlandt-Senge ◽  
Ulrich Müller
Keyword(s):  
Crown Ether ◽  
Crystal Structures ◽  
Monoclinic Space Group ◽  
Sodium Ions ◽  
X Ray Diffraction ◽  
Triclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Positional Disorder ◽  
Cl Atoms

The title compounds were obtained from NiS + PPh4Cl + HCl in dichloromethane, from NiCl2 and PPh4Cl and from NiCl2 + Na2S + 15-crown-5 in acetonitrile or CH2Cl2, respectively. Their crystal structures were determined by X-ray diffraction. (PPh4)2[NiCl4]: monoclinic, space group C 2/c, Z = 4, a = 1094.9(3), b = 1946.1(4), c = 2033.5(5) pm, β = 91.48(3)°; R = 0.07 for 2895 unique observed reflexions. [Na-15-crown-5]2[NiCl4]: triclinic, space group P1̄, Z = 2, a = 987.6(1), b = 998.0(1), c = 1779.9(2) pm, α = 104.17(1), β = 95.43(1), γ = 109.95(1)°; R = 0.090 for 4155 unique observed reflexions. In both cases, the [NiCl4]2- ions have distorted tetrahedral structures. With PPh4+ as the cation the distortion corresponds to a twisted tetrahedron which fulfils the point symmetry D2, the deviation from a flattened D2d-tetrahedron being small. In (PPh4)2[NiCl4] cations and anions alternate in layers parallel to (001). In [Na-15-crown-5]2[NiCl4] two of the Cl atoms of the anion are coordinated to sodium ions; one of the crown ether molecules shows positional disorder.

Crystal structures of two lactones of the bicyclo[2,2,2]octane series

1982 ◽  
Vol 35 (2) ◽  
pp. 457 ◽  
Author(s):  
RM Carman ◽  
SS Smith ◽  
CHL Kennard ◽  
G Smith ◽  
AH White ◽  
...  
Keyword(s):  
Least Squares ◽  
Crystal Structures ◽  
Three Dimensional ◽  
Direct Methods ◽  
Monoclinic Space Group ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray ◽  
A Cell

The crystal structures of two γ-lactones of the bicyclo[2,2,2]octane series, endo-3-carboxy-exo-5- iodobicyclo[2,2,2]octane-2,6-carbolactone (2; R = CO2H) and exo-3-methoxycarbonyl-endo-5-acetoxybicyclo[2,2,2] octane-2,6-carbolactone (7b), have been determined by direct methods from three-dimensional X-ray data and refined by least-squares to final residuals of 0.033 (2; R = CO2H) and 0.036 (7b) for 1918 and 630 'observed' reflections respectively. Crystals for (2; R = CO2H) are monoclinic, space group P21/c with Z 8 in a cell of dimensions a 7.192(2), b 23.785(8), c 13.199(5) �, β 105.35(2)�, while (7b) crystallizes in the orthorhombic space group P212121 with Z 4 in a cell of dimensions a 13.347(7), b 11.839(7), c 8.227(11) �.

Temperature phase changes in solid bicyclo[3.3.1]nonane-2,6-dione and bicyclo[3.3.1]nonane-3,7-dione from powder X-ray diffraction data

2007 ◽  
Vol 40 (4) ◽  
pp. 702-709 ◽  
Author(s):  
Michela Brunelli ◽  
Marcus A. Neumann ◽  
Andrew N. Fitch ◽  
Asiloé J. Mora
Keyword(s):  
Simulated Annealing ◽  
Crystal Structures ◽  
Phase Ii ◽  
Diffraction Data ◽  
Direct Methods ◽  
Temperature Phase ◽  
Molecular Orbital Calculations ◽  
X Ray Diffraction ◽  
Space Group ◽  
X Ray

The crystal structures of bicyclo[3.3.1]nonane-2,6-dione and bicyclo[3.3.1]nonane-3,7-dione have been solved by direct methods and by direct-space simulated annealing, respectively, from powder synchrotron X-ray diffraction data. Both compounds have a transition to a face-centred-cubic orientationally disordered phase (phase I) near 363 K, as shown by differential scanning calorimetry and powder diffraction measurements. Phase II of bicyclo[3.3.1]nonane-2,6-dione, which occurs below 363 K, is monoclinic, space groupC2/c, witha= 7.38042 (4),b= 10.38220 (5),c= 9.75092 (5) Å and β = 95.359 (1)° at 80 K. Phase II of bicyclo[3.3.1]nonane-3,7-dione, which occurs below 365 K, is tetragonal, space groupP41212, witha= 6.8558 (1) andc= 16.9375 (1) Å at 100 K. This phase coexists in a biphasic mixture with a minor monoclinic phase II′ [a= 11.450 (6),b = 20.583 (1),c= 6.3779 (3) Å, β = 94.7555 (5)°, at 100 K] detected in the sample, which impeded indexing with standard programs. The crystal structures of phases II were solved by direct methods and by direct-space simulated annealing, employing powder synchrotron X-ray diffraction data of increased instrumental intensity and resolution from the ID31 beamline at the ESRF, and novel indexing algorithms.Ab initiomolecular orbital calculations on the two systems are reported. In the solid state, the molecules pack in chair–chair conformation; molecular structures and packing are discussed.

Cyclometallated Compounds. IX. Reactions of 2-Benzoylpyridine With Rhodium(III) Trichloride

1995 ◽  
Vol 48 (9) ◽  
pp. 1573 ◽  
Author(s):  
DJ Degeest ◽  
PJ Steel
Keyword(s):  
Crystal Structure ◽  
Crystal Structures ◽  
The Other ◽  
Reaction Conditions ◽  
Initial Product ◽  
X Ray ◽  
X Ray Crystallography

X-Ray crystallography and n.m.r. spectroscopy have been used to study the products of reactions between rhodium(III) trichloride and 2-benzoylpyridine under various reaction conditions. X-Ray crystal structures have shown that the initial product of reaction in refluxing ethanol is a centrosymmetric isomer, as previously proposed, but that this undergoes aqueous hydrolysis to a C2-symmetric isomer, rather than the previously proposed C2v isomer. Reaction in refluxing 2-methoxyethanol produces an unusual complex with one C-N cyclometallated ligand and one N-O coordinated ligand. In Me2SO, the non-cyclometallated ligand of this latter compound undergoes solvolysis to produce a complex containing two Me2SO molecules, one coordinated through oxygen and the other through sulfur. The X-ray crystal structure of this compound is also reported.

Synthesis and characterization of [MII(bqb)] (M = Co, Ni, Cu), [N(n-Bu)4][CoIII(bqb)(CN)2], and [N(n-Bu)4][CoIII(bqb)(N3)2] containing deprotonated N,N'-bis(2-quinolinecarboxamide)-1,2-benzene (bqb) – X-ray crystal structures of [NiII(bqb)] and [N(n-Bu)4][CoIII(bqb)(N3)2]

2006 ◽  
Vol 84 (7) ◽  
pp. 971-978 ◽  
Author(s):  
Soria Meghdadi ◽  
Mehdi Amirnasr ◽  
Vratislav Langer ◽  
Alison Zamanpoor
Keyword(s):  
Crystal Structures ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
X Ray Crystallography ◽  
H Nmr ◽  
Square Planar ◽  
Distorted Octahedral ◽  
Elemental Analyses

Cobalt(II), nickel(II), copper(II), and two cobalt(III) complexes of a new dianionic ligand, bqb, [H2bqb = N,N'-bis(2-quinolinecarboxamide)-1,2-benzene] have been synthesized and characterized by elemental analyses, IR, and 1H NMR spectroscopy. The crystal and molecular structures of the [Ni(bqb)] (2) and [N(n-Bu)4][CoIII(bqb)(N3)2] (5) complexes were determined by X-ray crystallography. Complex 2 crystallizes in the monoclinic space group C2/c with a distorted square-planar structure including two short Ni–N (1.848 Å) and two long Ni–N (1.958 Å) bonds. The structure consists of sheets formed in the plane parallel to the b axis and diagonal to vectors a and c by intermolecular hydrogen bonds. Complex 5 crystallizes in the monoclinic space group C2 with a distorted octahedral structure. The [N(n-Bu)4]+ ion is disordered at the C3A and C4A atoms of one Bu. The IR and 1H NMR spectra of the complexes are also discussed.Key words: N4-dianionic amido ligand (bqb), (bqb) complexes of Co(II), Ni(II), Cu(II), and Co(III), azide, cyanide, X-ray crystal structures.

Crown Ether Complexes of Sulfonium Salts—The X-Ray Crystal Structures of[PhCOCH2SMe2·[18]Crown-6]n[PF6]n and[(PhCOCHPhSMe2)2·[18]Crown-6][PF6]2

1984 ◽  
Vol 23 (12) ◽  
pp. 977-979 ◽  
Author(s):  
Billy L. Allwood ◽  
John Crosby ◽  
David A. Pears ◽  
J. Fraser Stoddart ◽  
David J. Williams
Keyword(s):  
Crown Ether ◽  
Crystal Structures ◽  
Sulfonium Salts ◽  
X Ray ◽  
Crown Ether Complexes
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