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.

Organoamido- and Aryloxo-Lanthanoids. XI. Syntheses and Crystal Structures of Nd(Odpp)3, Nd(Odpp)3(thf) and [Nd(Odpp)3(thf)2].2(thf) (Odpp-=2,6-Diphenylphenolate): Variations in Intramolecular π-Ph-Nd Interactions

1995 ◽  
Vol 48 (4) ◽  
pp. 741 ◽  
Author(s):  
GB Deacon ◽  
TC Feng ◽  
BW Skelton ◽  
AH White
Keyword(s):  
Crystal Structure ◽  
Crystal Structures ◽  
Phenyl Group ◽  
Triangular Array ◽  
The Other ◽  
X Ray ◽  
Trigonal Bipyramidal ◽  
Distorted Trigonal Bipyramidal

The X-ray crystal structure of Nd (Odpp)3 ( Odpp- = 2,6-diphenylphenolate), obtained by sublimation of Nd ( Odpp )3( thf )2 ( thf = tetrahydrofuran ) [triclinic, Pī , a 15.835(5), b 13.499(10), c 10.955(11) Ǻ, α 116.25(7), β 92.87(7), γ 101.66(6)°, V 2031 Ǻ3, Z2, No 5726 'observed' data (I > 3σ(I)) refined to conventional R 0.047 shows a near triangular array of oxygens surrounding neodymium { Nd -O} 2.169 Ǻ, ∑ O- Nd -O 353.2° with additional, intramolecular Nd-η6-Ph chelate interactions { Nd -C} 3.046 Ǻ and Nd-η1-Ph ( Nd -C 2.964(7)Ǻ). There is a pseudotrigonal bipyramidal arrangement of the oxygens, the centroid of the η6-Ph, and the η1-carbon. The complex Nd ( Odpp )3( thf ), obtained by crystallization of Nd ( Odpp )3( thf )2 from toluene (monoclinic, P21/c, a 12.213(4), b 21.447(4), c 17.744Ǻ, β 104.25(2)°, V 4505 Ǻ3, Z 4, R 0.042 for No 8014) also has pseudotrigonal bipyramidal stereochemistry, with a triangular equatorial array of aryl oxide oxygens { Nd -O} 2.193 Ǻ; ∑ O- Nd -O 358.7°, an apical thf oxygen (Nd -O 2.446(3)Ǻ), and an apical intramolecular chelating phenyl group. As the last has three Nd -C contacts (3.094(5), 3.144(5), 3.010(5)Ǻ) significantly shorter than the other three (3.300(5), 3.427(5), 3.377(5)Ǻ), an η3-Ph-Nd interaction seems likely. For [ Nd ( Odpp )3( thf )2].2( thf ), obtained by crystallization from tetrahydrofuran without drying of the crystals, the X-ray structure (monoclinic, P21, a 10.230(2), b 21.919(5), c 13.411(4) Ǻ, β 101.15(2)°, V 2950 A3, Z2, R 0.058 for No 3237) reveals a distorted trigonal bipyramidal arrangement of three aryl oxide oxygens (two equatorial 2.208(9), 2.16(1) Ǻ; one axial 2.203(9) Ǻ) and two thf oxygens (one equatorial 2.44(1) Ǻ; one axial (significantly distant) 2.62(1) Ǻ). The X-ray structure of [La( Odpp )3( thf )2].2( thf ) shows it to be isostructural with the neodymium analogue.

scholarly journals Azo-linked corner porphyrin systems: synthesis, crystal structures and spectroscopic investigation

2010 ◽  
Vol 14 (06) ◽  
pp. 481-493 ◽  
Author(s):  
Bruno Bašić ◽  
John C. McMurtrie ◽  
Dennis P. Arnold
Keyword(s):  
Crystal Structure ◽  
Crystal Structures ◽  
Spectroscopic Investigation ◽  
The Other ◽  
X Ray ◽  
Tert Butyl ◽  
Dinitro Derivative

1,2-bis[10,15-di(3,5-di-tert-butyl)phenylporphyrinatonickel(II)-5-yl]diazene was synthesised via copper-catalyzed coupling of aminated nickel(II) 5,10-diarylporphyrin ("corner porphyrin") and its X-ray crystal structure was determined. Two different crystals yielded different structures, one with the free meso-positions in a trans-like orientation, and the other with a cis-like disposition. The free meso-positions of the obtained dimer have been further functionalized while the synthesis of a zinc analog has so far been unsuccessful. The X-ray crystal structure of the dinitro derivative of the dinickel(II) azoporphyrin was determined, and the structure showed a cis-like disposition of the nitro groups.

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.

Synthesis and structural study of aminals derived from 8-aminoquinoline and 1-aminonaphtalene

1987 ◽  
Vol 65 (4) ◽  
pp. 687-692 ◽  
Author(s):  
Enrique Galvez ◽  
Isabel Iriepa ◽  
Antonio Lorente ◽  
Jose Miguel Mohedano ◽  
Feliciana Florencio ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Carbon Atom ◽  
Mass Spectra ◽  
The Other ◽  
Reaction Conditions ◽  
Schiff’S Base ◽  
Triclinic Space Group ◽  
X Ray ◽  
H Nmr ◽  
Cell Dimensions

Reaction of 8-aminoquinoline with pyridine-2-carboxaldehyde (2), pyridine-3-carboxaldehyde (3), pyridine-4-carboxaldehyde (4), and benzaldehyde (5) yields the corresponding aminals or Schiff's bases according to reaction conditions; analogous results are obtained from the reaction of 1-amino-naphtalene with pyridine-2-carboxaldehyde (6). On the other hand, reaction of 8-aminoquinoline with thiophene-2-carboxaldehyde or pyrrole-2-carboxaldehyde yields neither the aminal nor the Schiff's base. Crystals of 4 (C24H19N5) belong to the triclinic space group [Formula: see text]. Cell dimensions are a = 11.547(3), b = 11.759(2), c = 15.687(5) Å, α = 98.50(2)°, β = 101.61(2)°, γ = 107.28(2)°, V = 1942.6(9) Å3. Final R = 0.077 and Rw = 0.064; 3160 reflections were observed. The ir, 1H nmr of 2–6, the mass spectra of 4 and 5 and the X-ray analysis of 4 are described and discussed. Preparative features, ir, 1H nmr, analyses and crystal structure indicate that the formation of 2–6 are governed mainly by the nucleophilicity at the aldehyde carbon atom and the existence of the hydrogen bonds in the aminal.

Temperature dependence of crystal structure of NaK0.72(NH4)0.28(+)-C4H4O6.4H2O in the paraelectric phase

1996 ◽  
Vol 52 (6) ◽  
pp. 976-981 ◽  
Author(s):  
E. Suzuki ◽  
H. Kabasawa ◽  
T. Honma ◽  
R. Nozaki ◽  
Y. Shiozaki
Keyword(s):  
Crystal Structure ◽  
Structural Change ◽  
Temperature Dependence ◽  
Crystal Structures ◽  
Paraelectric Phase ◽  
The Other ◽  
Carboxylate Anion ◽  
Water Molecules ◽  
Crystal Data ◽  
X Ray

The crystal structures of the ferroelectric NaK0.72 (NH4)0.28(+)-C4H4O6.4H2O (RS0.72ARS0.28) have been studied in the paraelectric phase [Mr = 276.32, orthorhombic, P21212,° Z = 4, F(000) = 575.04, λ(Mo Kα1) = 0.70926 Å]; T = 213 (1), 253 (1) and 293 (1) K. The crystal data are as follows: (I) at T = 213 (1) K: R = 0.0424, wR = 0.0399, number of reflections = 3414, a = 11.899 (2), b = 14.273 (2), c = 6.211 (1) Å, V = 1054.9 (2) Å3, Dx = 1.740 g cm−3; (II) at T = 253 (1) K: R = 0.0498, wR = 0.0442, number of reflections = 3284, a = 11.929 (1), b = 14.297 (1), c = 6.221 (1) Å, V = 1061.0 (2) Å3, Dx = 1.730 g cm−3; (III) at T = 293 (1) K: R = 0.0473, wR = 0.0392, number of reflections = 3179, a = 11.955 (1), b = 14.317 (1), c = 6.231 (1) Å, V = 1066.5 (1) Å3, Dx = 1.721 g cm−3. X-ray investigations reveal details of structural change with temperature in the paraelectric phase. The carboxylate anion O(3)—C(4)—O(4) in the tartrate molecule is displaced along the a axis as the temperature decreases; moreover, the O(8) atom is displaced in the opposite direction against the shift of the carboxylate anion. The temperature dependence of the thermal motions of O(8) shows different behavior from the other O atoms of the water molecules. The amplitude of the thermal motion of O(8) does not tend to zero at T = 0 K, while the other O atoms of the water molecules tend to zero.

Heteronukleare Komplexverbindungen mit Metall–Metall-Bindungen, V [1] / Heteronuclear Co-ordination Compounds with Metal–Metal-Bonds, V [1]

1991 ◽  
Vol 46 (4) ◽  
pp. 507-518 ◽  
Author(s):  
Ralf Fuchs ◽  
Peter Klüfers
Keyword(s):  
Crystal Structure ◽  
The Other ◽  
Dinuclear Complex ◽  
Carbonyl Complex ◽  
Tetrahedral Geometry ◽  
X Ray ◽  
X Ray Crystallography ◽  
Metal Metal ◽  
Cobalt Compounds ◽  
Metal Bonds

The heteronuclear carbonyl complex [(NH3)2CuCo(CO)4] 1 reacts with the phosphane ligands PPh3, PEt3 and P(OMe)3. A dinuclear complex, [(PPh3),CuCo(CO)4] 2, is formed with PPh3, while trinuclear anionic [Cu{Co(CO)4}2]- species are formed with the other phosphane ligands. The crystal structure of 2 (Cu—Co = 255.2(2) pm) and the structures of two compounds with trinuclear anions, [Cu{P(OMe)3}4][Cu{Co(CO)4}2] 3 (Cu—Co = 232.64(8) and 233.10(8) pm) and PPN[Cu{Co(CO)4}2] 6 (Cu—Co = 238.1(1) and 234.3(1) pm), have been determined by X-ray crystallography. The angle Cax—Co—Ceq of tetracarbonyl cobalt compounds (i. e. the deviation from tetrahedral geometry) depends on the charge of the Co(CO)4 fragment, as calculated with the electronegativity equalization scheme of Bratsch (J. Chem. Ed. 61, 588 (1984)).

Ruthenium carbonyl complexes. III. Peparations, properties and structures of Dicarbonyl- and Monocarbonyl-(2,2':6',2''-terpyridyl)ruthenium(II) complexes

1984 ◽  
Vol 37 (5) ◽  
pp. 929 ◽  
Author(s):  
GB Deacon ◽  
JM Patrick ◽  
BW Skelton ◽  
NC Thomas ◽  
AH White
Keyword(s):  
Crystal Structure ◽  
Crystal Structures ◽  
Room Temperature ◽  
Chloro Complex ◽  
Carbonyl Complexes ◽  
X Ray ◽  
X Ray Crystallography ◽  
Ruthenium Carbonyl

Reaction of 2,2':6',2''-terpyridyl (tpy) with ruthenium dicarbonyl dihalides yields the complexes Ru(CO)2X2(tpy) (X = Br or Cl), which can be protonated giving [Ru(CO)2X2(tpyH)]ClO4. Crystal structures of the two forms (red and yellow) of Ru(CO)2Br2(tpy) show each to have octahedral stereo-chemistry with cis-carbonyls, trans-bromines, and bidentate tpy. Treatment of Ru(CO)2X2(tpy) complexes with trimethylamine N-oxide in dichloromethane at room temperature gives cis-Ru(CO)X2(tpy) complexes. The presence of cis halogens and tridentate terpyridyl in the chloro complex has been established by X-ray crystallography. Reaction of terpyridyl with ruthenium trichloride in dimethylformamide yields trans-Ru(CO)Cl2(tpy), the crystal structure of which has been determined.

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.

scholarly journals Crystal structure of glutamate-1-semialdehyde-2,1-aminomutase fromArabidopsis thaliana

2016 ◽  
Vol 72 (6) ◽  
pp. 448-456 ◽  
Author(s):  
Yingxian Song ◽  
Hua Pu ◽  
Tian Jiang ◽  
Lixin Zhang ◽  
Min Ouyang
Keyword(s):  
Crystal Structure ◽  
Arabidopsis Thaliana ◽  
Function Analysis ◽  
The Other ◽  
Negative Cooperativity ◽  
Higher Plant ◽  
X Ray ◽  
X Ray Crystallography ◽  
Cofactor Binding ◽  
Asymmetric Dimer

Glutamate-1-semialdehyde-2,1-aminomutase (GSAM) catalyzes the isomerization of glutamate-1-semialdehyde (GSA) to 5-aminolevulinate (ALA) and is distributed in archaea, most bacteria and plants. Although structures of GSAM from archaea and bacteria have been resolved, a GSAM structure from a higher plant is not available, preventing further structure–function analysis. Here, the structure of GSAM fromArabidopsis thaliana(AtGSA1) obtained by X-ray crystallography is reported at 1.25 Å resolution.AtGSA1 forms an asymmetric dimer and displays asymmetry in cofactor binding as well as in the gating-loop orientation, which is consistent with previously reportedSynechococcusGSAM structures. While one monomer binds PMP with the gating loop fixed in the open state, the other monomer binds either PMP or PLP and the gating loop is ready to close. The data also reveal the mobility of residues Gly163, Ser164 and Gly165, which are important for reorientation of the gating loop. Furthermore, the asymmetry of theAtGSA1 structure supports the previously proposed negative cooperativity between monomers of GSAM.

A topochemical rearrangement with multiple inversions of configuration

2001 ◽  
Vol 79 (8) ◽  
pp. 1272-1277 ◽  
Author(s):  
Saul Wolfe ◽  
Yih-Huang Hsieh ◽  
Raymond J Batchelor ◽  
Frederick WB Einstein ◽  
Ian D Gay
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Room Temperature ◽  
The Other ◽  
X Ray ◽  
Controlled Processes ◽  
X Ray Crystallography ◽  
Intramolecular Process ◽  
C Nmr ◽  
The Ideal

Crystalline 2-benzyloxypyridine-1-oxide rearranges slowly at room temperature to crystalline 1-benzyloxy-2-pyridone. No intermediates are detected when the process is followed by solid-state 13C NMR. The crystal structure of the pyridine-1-oxide strongly suggests that a topochemically controlled intramolecular process, in which the benzyl group migrates with retention of configuration, is not feasible. On the other hand, although somewhat disfavoured by initial solid-state O···C···O angles significantly less than the ideal 180°, intermolecular topochemically controlled processes can be envisaged that lead, with multiple inversions of configuration, either to net retention of configuration or to net inversion of configuration in the benzyl group. In contrast to the 50–80% inversion observed in solution, in the solid state only inversion is observed experimentally when chirally labelled α-deuteriobenzyloxypyridine-1-oxide is allowed to rearrange.Key words: X-ray crystallography, solid-state 13C NMR, benzyl-α-D-alcohol, 2-benzyloxypyridine-1-oxide, 1-benzyloxy-2-pyridone.

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