Zur Chemie der 1,3,5-Triaza-2-phosphorinan-4,6-dione. Teil IX. Umsetzungen einiger 1,3,5-Triorgano-1,3,5-triaza-2λ3-phosphorinan-4,6-dione mit Hexafluoraceton / Chemistry of the 1,3,5-Triaza-2-phosphorinan-4,6-diones. Part IX. Reaction of some 1,3,5-Triorgano-1,3,5-triaza-2λ3-phosphorinan-4,6-diones with Hexafluoroacetone

1995 ◽  
Vol 50 (12) ◽  
pp. 1785-1790 ◽  
Author(s):  
Ion Neda ◽  
Michael Farkens ◽  
Axel K. Fischer ◽  
Peter G. Jones ◽  
Reinhard Schmutzler
Keyword(s):  
Crystal Structure ◽  
Phosphorus Atom ◽  
Mass Spectra ◽  
Membered Ring ◽  
The Other ◽  
X Ray ◽  
Trigonal Bipyramidal ◽  
Phosphoryl Compound ◽  
Spirocyclic Compounds

The reactions of 2-(2-chloroethyl)amino-1,5-dimethyl-3-phenyl-1,3,5-triaza-2λ3-phosphorinan- 4,6-dione (1), 2-bis(2-chloroethyl)amino-1,5-dimethyl-3-phenyl-1,3,5-triaza-2A3-phosphorinan- 4,6-dione (2), 2-methoxy-1,3,5-trimethyl-1,3,5-triaza-2λ3-phosphorinan-4,6-dione (3) and 2-trimethylsiloxy-1,3,5-trimethyl-1,3,5-triaza-2λ3-phosphorinan-4,6-dione (5) with hexafluoracetone are described. In the case of 2 and 3 the reaction furnished the spirocyclic compounds 7 and 8. 2-Bis(2-chloroethyl)amino-1,3,5-triphenyl-1,3,5-triaza-2λ3-phosphorinan- 4,6-dione (4) did not react. In the case of 1 and 5 rearrangement reactions took place; the (2-chloroethyl)amino substituent of 1 reacted with one of two equivalents of hexafluoroacetone with formation of the spirocyclic phosphorane 6. The reaction of 5 with tetrabromoorthobenzoquinone gave the phosphoryl compound 9. Compounds 6 - 8 were characterized via their 1H-, 13C-, 19F- and 31P-NMR and mass spectra, compound 9 via its 1H-, 13C- and 31P-NMR and mass spectra. An X-ray crystal structure determination of 8 was conducted; in the six-membered ring the phosphorus atom lies 73 pm out of the plane of the other atoms, and displays trigonal bipyramidal coordination.

Synthese von vier- und achtgliedrigen Heterocyclen, die Schwefel, Stickstoff und Phosphor enthalten, und die Röntgenstrukturanalyse eines phosphorhaltigen achtgliedrigen SN-Ringes / Synthesis of Four- and Eight-Membered Heterocycles Containing Sulfur, Nitrogen and Phosphorus and the X-ray Structure of a Phosphorus-Containing Eight-Membered SN-Ring

1980 ◽  
Vol 35 (9) ◽  
pp. 1130-1136 ◽  
Author(s):  
Herbert W. Roesky ◽  
Sushil K. Mehrotra ◽  
Christoph Platte ◽  
Djamrnschid Amirzadeh-Asl ◽  
Bernhard Roth
Keyword(s):  
Tertiary Amine ◽  
Phosphorus Atom ◽  
Mass Spectra ◽  
Phosphorus Pentachloride ◽  
Membered Ring ◽  
Phosphonium Salts ◽  
Nitrogen And Phosphorus ◽  
Orthorhombic Space Group ◽  
X Ray ◽  
Phosphorus Containing

Eight-membered rings of the composition [SO2(NR)2PR′]2 3a-d with R = CH3, C2H5, and R′ = CH3, C6H5, were prepared from substituted sulfamides and dichlorophosphanes in the presence of a tertiary amine. These molecules were characterized on the basis of 1H and 31P NMR investigations and of mass spectra. 3 a reacts with phosphorus pentachloride to yield the spirocyclic derivative 4 with the phosphorus atom in the center of two four-membered rings. Methyliodide reacts with 3 a and 3 b under opening of the eight- membered ring and formation of phosphonium salts. The structure of 3 b is discussed in detail. 8b crystallizes in the orthorhombic space group Pna 21 with a = 12.60(0), b = 13.27(1), c = 12.62(4) Å.

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.

Reactions of the tetrasulfur pentanitride(-1) ion with halogens: synthesis, spectroscopic characterization, and crystal structure of pentasulfur hexanitride

1979 ◽  
Vol 57 (11) ◽  
pp. 1286-1293 ◽  
Author(s):  
T. Chivers ◽  
J. Proctor
Keyword(s):  
Crystal Structure ◽  
Thionyl Chloride ◽  
Mass Spectra ◽  
Methylene Chloride ◽  
Spectroscopic Characterization ◽  
The Other ◽  
X Ray ◽  
Yellow Orange ◽  
Uv Visible ◽  
Single Bonds

Pentasulfur hexanitride, S5N6, has been prepared in good yield by the reaction of [n-Bu4N+][S4N5−] with bromine (or iodine) in methylene chloride at 0 °C. In contrast, the tetrasulfur pentanitride(−1) ion reacts smoothly with chlorine to give S4N5Cl, while the reaction with sulfuryl chloride produces S4N5Cl and S5N6 and the reaction with thionyl chloride produces a mixture of S3N2O, S3N2O2, S4N4, and S5N6. Pentasulfur hexanitride is an air-sensitive, explosive, yellow-orange solid which sublimes at ca. 45 °C/10−2 Torr without significant decomposition. It has been characterised by infrared, Raman, uv–visible, and mass spectra and by a single crystal X-ray structure determination. The crystals are monoclinic and belong to the space group C2/c, a = 8.787(2), b = 11.190(2), c = 7.427(2) Å, β = 106.46(2)°, V = 700.3(5) Å3, Z = 4, Dc = 2.317 g cm−3. The refined structure (Rw = 0.040) has twofold symmetry and resembles a basket in which an —N=S=N— unit (d(S—N) = 1.54 Å) is the handle which bridges an S4N4 cradle via S—N single bonds (d(S—N) = 1.70 Å). The introduction of this bridge widens one of the [Formula: see text] transannular separations in S4N4 to 3.94 Å while the other is shortened to 2.43 Å. Thus, the S4N4 cradle can be viewed as two five-membered rings fused at the S—S bond.

Organoamido- and Aryloxo-lanthanoids. X. Tris(η2-3,5-di-t-butylpyrazolato)lanthanoid(III) Complexes and the X-Ray Crystal Structure of Er(η2-But2pz)3(thf)2

1994 ◽  
Vol 47 (7) ◽  
pp. 1223 ◽  
Author(s):  
JE Cosgriff ◽  
GB Deacon ◽  
BM Gatehouse ◽  
H Hemling ◽  
H Schumann
Keyword(s):  
Crystal Structure ◽  
Triphenylphosphine Oxide ◽  
The Other ◽  
Monoclinic Space Group ◽  
Space Group ◽  
X Ray ◽  
Trigonal Bipyramidal ◽  
Oxygen Atoms

The complexes Ln (But2pz)3( thf )2 ( Ln = Y, La, Pr, Nd , Sm, Gd, Dy , Er , Yb, Lu; But2pz- = 3,5-di-t-butylpyrazolate; thf = tetrahydrofuran ), and [ Ln (But2pz)3(OPPh3)2].( dme )n ( Ln = La, n = ⅔ ; Ln = Er , n = 1; dme = 1,2-dimethoxyethane) have been prepared by reaction of the lanthanoid metal with bis ( pentafluorophenyl )mercury and the corresponding pyrazole in either thf , or in dme in the presence of triphenylphosphine oxide. The X-ray crystal structure of Er (η2-But2pz)3( thf )2 [monoclinic, space group P21 (No. 4), a 9.738(4), b 19.602(4), c 11.636(4) Ǻ, β 99.42(3)°, R 0.0374 for 3667 observed reflections] shows the complex to be an eight-coordinate monomer with three chelating But2pz ligands . The arrangement of centres ( Cen ) of the N-N bonds of the But2pz ligands [< Er -N> 2.336 Ǻ; Cen-Er-Cen 140.1(4)°, 110.3(4)° and 109.6(4)°] and the thf oxygen atoms [< Er -O> 2.351 Ǻ; O- Er -O 140.1(4)°] is intermediate between trigonal bipyramidal and square pyramidal. The other Ln (But2pz)3( thf )2 complexes and Ln (But2pz)3(OPPh3)2 are considered to have similar structures.

Tris [(trimethylsilyl)oxy] antimony

1994 ◽  
Vol 49 (7) ◽  
pp. 855-858 ◽  
Author(s):  
Michael Baier ◽  
Klaus Angermaier ◽  
Hubert Schmidbaur
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Gas Phase ◽  
Structure Determination ◽  
Spectroscopic Data ◽  
Mass Spectrometric ◽  
Unit Cell ◽  
The Other ◽  
X Ray ◽  
Trigonal Bipyramidal

Abstract Tris[(trimethylsilyl)oxy]antimony (Sb(OSiMe3)3, 1) has been prepared from SbCl3 and 3 equiv. of LiOSiMe3 in diethylether. According to mass spectrometric and NMR spectroscopic data, 1 appears to be a monomer in solution and in the gas phase. Dimerisation occurs, however, in the solid state as verified by an X-ray crystal structure determination. The unit cell contains three crystallographically independent monomers, two of which form one type of dimer, while the other is part of a centrosymmetrical dimer. In both types of dimers two Sb atoms are connected via two OSiMe3 groups to form distorted Sb2O2-squares. Together with the remaining 4 OSiMe3 groups and the two stereochemically active lone pairs, each Sb exhibits a trigonal bipyramidal coordination.

scholarly journals Molekül- und Kristallstruktur des 1.5-Dichlor-3.7-bis(trifluormethyl)-4.8-bis(2′.6′-dimethylphenyl)-2.6.9-trioxa- 4.8-diaza-1.5-diborabicyclo [3.3.1] nonadiens / Molecular and Crystal Structure of 1,5-Dichloro-3,7-bis(trifluoromethyl)-4,8-bis(2′,6′-dimethylphenyl)-2,6,9-trioxa-4,8-diaza- 1,5-diborabicyclo[3,3,1 ]nonadiene

1980 ◽  
Vol 35 (12) ◽  
pp. 1499-1502 ◽  
Author(s):  
William Clegg ◽  
Mathias Noltemeyer ◽  
George M. Sheldrick ◽  
Walter Maringgele ◽  
Anton Meller
Keyword(s):  
Crystal Structure ◽  
Title Compound ◽  
Membered Ring ◽  
The Other ◽  
Molecular And Crystal Structure ◽  
Compound A ◽  
Space Group ◽  
X Ray

The structure of the title compound (a = 1185.4, b = 1197.7, c = 1764.8 pm, β = 73.96°, space group P21/c) has been determined from X-ray diffractometer data. The molecule is structurally analogous to the tetraborate ion [B4O7]2-. The eight-membered ring is folded by 104° about the B - B vector. The boron atoms are more strongly bonded to the bridging oxygen [B-O(B) 139 pm] than to the other atoms [B-O(C) 155 pm, B-N 160 pm, B-Cl 182 pm].

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.

Reaktionen von 1,2,4-Thiadiazol-3,5-dicarbonitril mit Schwefelchloriden: Röntgenstrukturanalyse von S3(CN)4Cl2·AsF5 und S3(CN)8Cl2/Reactions of 1,2,4-Thiadiazol-3,5-dicarbonitrile with Sulfur Chlorides: X-Ray Crystal Structure Analysis of S3(CN)4Cl2·A sF5 and S3(CN)8Cl2

1986 ◽  
Vol 41 (2) ◽  
pp. 162-166 ◽  
Author(s):  
Herbert W. Roesky ◽  
Jörg Sundermeyer ◽  
Jürgen Schimkowiak ◽  
Thomas Gries ◽  
Mathias Noltemeyer ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Nitrogen Atom ◽  
Sulfur Atom ◽  
Experimental Error ◽  
Crystal Structure Analysis ◽  
The Other ◽  
Space Group ◽  
X Ray ◽  
Ring Nitrogen

The reactions between 1,2,4-thiadiazol-3,5-dicarbonitrile, S(CN)4, and sulfur chlorides (SCl2 and S2Cl2) in the presence of Adogen® 464 (Aldrich) proceeds with formation of S3(CN)4Cl2 (1) and S3(CN)8Cl2 (2). These main products were characterized by X-ray structure determination of an adduct 1a and of 2. This adduct 1a was obtained by addition of the Lewis acid AsF5 in liquid SO2. 1a crystallizes with one SO2 molecule in the space group P21/n with a = 1177.3(2), b = 1082.8(1), c = 1255.3(5) pm, β = 109.73(3)°, Z = 4, V = 1.5061 nm3. It contains two five-membered rings connected by a nitrogen atom. AsF5 is coordinated to one of the ring nitrogen atoms [N(1)] adjacent to the sulfur atom S(1) and C(1)Cl-group. The other ring contains an S(2)-S(3) bond of length 207.7(4) pm. The rings are planar within experimental error. 2 crystallizes in the space group P21/n with a = 782.12(6), b = 1498.1(5), c = 1217.8(2) pm, β = 102.43(1)°, Z = 4, V = 1.3934 nm3. 2 is formed by addition of one molecule of SCl2 to two molecules of S(CN)4.

Zur Chemie der 1,3,5-Triaza-2-phosphorinan-4,6-dione. Teil X. Umsetzungen von 2-Hydro-1,3,5-trimethyl-1,3,5-triaza-2-oxo-2λ4- phosphorinan-4,6-dion mit Triazin-Derivaten sowie mit einigen Aldehyden / Chemistry of the 1,3,5-Triaza-2-phosphorinan-4,6-diones. Part X. Reactions of 2-Hydro-1,3,5-trimethyl-1,3,5-triaza-2-oxo-2λ4 -phosphorinan-4,6-dione with Triazine Derivatives and with Some Aldehydes

1995 ◽  
Vol 50 (12) ◽  
pp. 1833-1838 ◽  
Author(s):  
Ion Neda ◽  
Michael Farkens ◽  
Holger Thönnessen ◽  
Peter G. Jones ◽  
Reinhard Schmutzler
Keyword(s):  
Crystal Structure ◽  
Hydrogen Bonds ◽  
Structure Analysis ◽  
Mass Spectra ◽  
Nmr Spectra ◽  
Glyoxylic Acid ◽  
Crystal Structure Analysis ◽  
Membered Ring ◽  
X Ray ◽  
Triazine Derivatives

The reactions o f 2-hydro-1,3,5-trim ethyl-1,3,5-triaza-2-oxo-2λ4 -phosphorinan-4,6-dione 1 with the triazine derivatives, 1,3,5-trimethyl- and 1,3,5-tribenzyl-hexahydro-1,3,5-triazine, are described. The reaction of three equivalents of 1 with one equivalent of the triazine derivative gave 2 and 3. Both compounds were characterized via their 1H, 13C, and 31P NMR spectra, mass spectra and, in the case of 2, by an X-ray crystal structure analysis, which showed an almost planar six-membered ring; hydrogen bonds of the form N-H···O link the molecules in centrosymmetric pairs. The reactions of 1 with the aldehydes glyoxylic acid, 2-hydroxybenzaldehyde and 3,4,5-trimethoxybenzaldehyde gave addition products. The C (:O) group o f the aldehyde is inserted into the P -H bond o f 1. The resulting compounds 4 ,5 and 6 were characterized through their 1H, 13C, and 31P NMR spectra, and mass spectra.

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