The solid-state molecular structure of W(NO)3Cl3 and the nature of its W—NO bonding

2004 ◽  
Vol 82 (2) ◽  
pp. 285-292 ◽  
Author(s):  
Trevor W Hayton ◽  
Brian O Patrick ◽  
Peter Legzdins ◽  
W Stephen McNeil
Keyword(s):  
Molecular Structure ◽  
Solid State ◽  
Dft Calculations ◽  
Diffraction Analysis ◽  
Mirror Plane ◽  
Ambient Conditions ◽  
X Ray Diffraction ◽  
X Ray ◽  
Bond Lengths ◽  
Complex Solutions

The monomeric trinitrosyl complex, W(NO)3Cl3, can be prepared by the treatment of WCl6 in CH2Cl2 with NO gas, and its identity has been unambiguously confirmed by a single-crystal X-ray diffraction analysis. The complex crystallizes in the space group Pmn21 as a three-component twin (a = 10.4280(4) Å, b = 6.3289(2) Å, c = 5.6854(2) Å, Z = 2, R1 = 0.065, wR2 = 0.176). Its solid-state molecular structure consists of a tungsten centre bound to three chloride ligands and three linear nitrosyl ligands in a fac-octahedral stereochemistry. In addition, the structure contains a crystallographically imposed mirror plane. The two independent W—N linkages are 1.88(2) and 1.92(1) Å long, while the two corresponding N—O bond lengths are 1.13(2) and 1.16(2) Å. DFT calculations on fac-W(NO)3Cl3 at the B3LYP/LANL2DZ level of theory afford optimized intramolecular metrical parameters that match the X-ray crystallographically determined bond lengths and bond angles quite well. In addition, they provide a rationale for the nearly linear W-N-O linkages extant in the complex. Solutions of fac-W(NO)3Cl3 in CH2Cl2 lose ClNO under ambient conditions and deposit the well-known [W(NO)2Cl2]n polymer, and this conversion is fully reversible.Key words: nitrosyl, tungsten, structure, bonding.

Molecular and Crystal Structure of Chlorido[2-(N,N,N',N'- tetramethylamidinio)ethynido]silver

2013 ◽  
Vol 68 (5-6) ◽  
pp. 687-692
Author(s):  
Werner Weingärtner ◽  
Gerhard Maas
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Diffraction Analysis ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
Silver Complex ◽  
State Structure ◽  
X Ray Diffraction ◽  
X Ray ◽  
Bond Lengths

The solid-state structure of chlorido[2-(N,N,N',N'-tetramethylamidinio)ethynido]silver (3), obtained by C(sp)-metalation of N,N,N',N'-tetramethyl-propiolamidinium chloride with silver(I) oxide, has been determined by X-ray diffraction analysis. A comparison of bond lengths in the propiolamidinium moiety with those of the two genuine propiolamidinium salts 4 and 5, as well as with data for the isolated N,N,N',N'-tetramethyl-propiolamidinium cation obtained by quantum-chemical calculations, has been made. It can be concluded that complex 3 is better described as a (tetramethylamidinio) ethynyl than as a 3,3-bis(dimethylamino)allenylidene silver complex

scholarly journals 2.2.5.5-Tetraorganyl-1.4-dioxa-2.5-disilacyclohexane/2,2,5,5-Tetraorganyl-1,4-dioxa-2,5-disilacyclohexanes

1983 ◽  
Vol 38 (2) ◽  
pp. 190-193 ◽  
Author(s):  
Reinhold Tacke ◽  
Hartwig Lange ◽  
Anke Bentlage ◽  
William S. Sheldrick ◽  
Ludger Ernst
Keyword(s):  
Molecular Structure ◽  
Mass Spectrometry ◽  
Diffraction Analysis ◽  
X Ray Diffraction ◽  
X Ray ◽  
Elemental Analyses

Abstract The 2,2,5,5-tetraorganyl-1,4-dioxa-2,5-disilacyclohexanes 2a-2c were prepared by condensation of the corresponding (hydroxymethyl)diorganylsilanes 1 a-1 c. The constitution of the heterocycles was confirmed by elemental analyses, cryoscopic measurements, mass spectrometry, and NMR-spectroscopic (1H, 13C) investigations. The molecular structure of 2 b was determined by X-ray diffraction analysis.

A structural and carbon-nitrogen bond rotation study of N,N,N',N',2,2-hexamethylpropanediamide

1983 ◽  
Vol 36 (9) ◽  
pp. 1865 ◽  
Author(s):  
SF Lincoln ◽  
AM Hounslow ◽  
NJ Maeji ◽  
TW Hambley ◽  
MR Snow ◽  
...  
Keyword(s):  
Molecular Structure ◽  
Solid State ◽  
Kinetic Parameters ◽  
Methyl Groups ◽  
X Ray Diffraction ◽  
X Ray ◽  
Bond Rotation ◽  
Nitrogen Bonds ◽  
Rotation Study ◽  
Nitrogen Bond

The molecular structure of N,N,N',N',2,2-hexamethylpropanediamide has been determined in the solid state by X-ray diffraction methods. The structure of Me2NCOCMe2CONMe2 may be broadly described as two planar Me2NCO entities intersecting at the tetrahedral -CMe2- site. The angle between the normals to the two Me2NCO planes is 104.6�, and the two oxygen atoms are disposed outwards from the molecule and away from each other. Proton (270-MHz) n.m.r. studies yield k(320 K) 32.0 � 3.2 s-1, ΔH‡ 69.5 � 0.4 kJ mol-1 and ΔS‡ 0.6 � 1.1 J K-1 mol-1 for rotation of the N-methyl groups about the carbon-nitrogen bonds in CD3NO2 solution. Similar magnitudes for the kinetic parameters characterizing this process are obtained in CDCl3, and CD3CN solutions.

Darstellung und Struktur eines zweikernigen Vanadium(V)-Komplexes mit den terminal gebundenen Stickstoffliganden NtC4H9, NHtC4H9 und NH2tC4H9: [ VCl(μ-Cl)(NtC4H9)(NHtC4H9) (NH2tC4H9) ]2 / Synthesis and Molecular Structure of a Binuclear Vanadium(V) Complex Containing the Terminal Nitrogen Ligands NtC4H9, NHtC4H9, NH2tC4H9: [VCl(μ-Cl)(NtC4H9)(NHtC4H9)(NH2tC4H9)]2

1985 ◽  
Vol 40 (3) ◽  
pp. 363-367 ◽  
Author(s):  
Fritz Preuss ◽  
Edith Fuchslocher ◽  
William S. Sheldrick
Keyword(s):  
Molecular Structure ◽  
Diffraction Analysis ◽  
Vanadium Complex ◽  
X Ray Diffraction ◽  
X Ray ◽  
Nitrogen Ligands ◽  
Nmr Data ◽  
Distorted Octahedral ◽  
Tert Butylamine ◽  
Cl Atoms

tC4H9N = VCl2(NHtC4H9) and the tert-butylamine complex [tC4H9N=VCl2(NHtC4H9)(NH2tC4H9)] have been prepared by reaction of tC4H9N=VCl3 with NH2tC4H9. 1H and 51V NMR data of these compounds are reported. The complex was investigated by X-ray diffraction analysis; the structure has been found to be a binuclear vanadium complex bridged by two Cl-atoms with a distorted octahedral arrangement of the ligands.

Spaltung von S4N4 zu S2N2 bei Raumtemperatur: Darstellung und Struktur von S2N2 • 2AlBr3 / Cleavage of S4N4 to S2N2 at Room Tem perature: Preparation and Structure of S2N2 • 2AlBr3

1984 ◽  
Vol 39 (2) ◽  
pp. 145-148 ◽  
Author(s):  
Ulf Thewalt ◽  
Konrad Holl
Keyword(s):  
Molecular Structure ◽  
Room Temperature ◽  
Crystal And Molecular Structure ◽  
Crystal Data ◽  
X Ray Diffraction ◽  
X Ray ◽  
Bond Lengths

The compound S2N2 • 2AlBr3 has been prepared by reaction of S4N4 with AlBr3 in 1,2-dibromoethane at room temperature. Its crystal and molecular structure have been determined by X-ray diffraction; R = 0.068. Crystal data: monoclinic, P 21/n, a = 9.594(5), b = 9.975(4), c = 7.528(4) Å , β = 111.36(5)°. The S2N2 ring of the centrosymmetrical complex is bonded via its nitrogen atoms to two AlBr3 units thus completing coordination tetrahedra around the Al atoms. Bond distances and angles within the S2N2 ring are d(S-N) = 1.629(13) and 1.651(13) Å, ∢ (S-N-S) = 95.8, and ∢ (N-S-N) - 84.2°. Whereas the S-N bond lengths agree closely with those of free S2N2, the angle at N is enlarged by ca. 5° and the angle at S is decreased by ca. 5°. The sulfur atoms form two close S···Br contacts of length 3.149 (intramolecular) and 3.193 (intermolecular) Å , respectively. The intermolecular attractive nonbonded S···Br interactions tie the complexes together in a way that leads to infinite chains which run parallel to the crystallographic z axis

Bindung von Metall-Ionen an Dipeptide: Struktur von Thallium(I)-(3-benzyl-6-carboxylatomethyl-2,5-diketopiperazin) / Binding of Metal Ions by Dipeptides: Structure of Thallium(I) 3-Benzyl-6-carboxylatomethyl-2,5-diketopiperazine

1992 ◽  
Vol 47 (7) ◽  
pp. 952-956
Author(s):  
P. Mikulcik ◽  
P. Bissinger ◽  
J. Riede ◽  
H. Schmidbaur
Keyword(s):  
Solid State ◽  
Nitrogen Atom ◽  
Hydrogen Bonds ◽  
Diffraction Analysis ◽  
Carbonyl Oxygen ◽  
State Structure ◽  
X Ray Diffraction ◽  
X Ray ◽  
Crystalline Product ◽  
Oxygen Atoms

Ester cleavage of aspartame (L-α-aspartyl-L-phenylalanine methylester) (1), by equimolar quantities of thallium ethoxide is accompanied by intramolecular cyclisation to give thallium 3-benzyl-6-(carboxylatomethyl)-2,5-dioxopiperazine (2). The solid state structure of the crystalline product was determined by single-crystal X-ray diffraction analysis. The cations were found to form four short and four elongated contacts to seven oxygen atoms and one nitrogen atom of a total of six neighbouring 3-benzyl-6-(carboxylatomethyl)-2,5-dioxopiperazine anions. There are inter-anionic hydrogen bonds only between the imino groups and the carbonyl oxygen atoms (O3, O4), featuring a pattern similar to that found for cytosine-guanosine contacts in DNA.

Contributions to the Chemistry of Boron, 204 [1] An Unusual [2+2]-Cycloaddition Reaction of Dicobalt Octacarbonyl

1990 ◽  
Vol 45 (6) ◽  
pp. 828-832 ◽  
Author(s):  
Sreelatha Channareddy ◽  
Gerald Linti ◽  
Heinrich Nöth
Keyword(s):  
Diffraction Analysis ◽  
Cycloaddition Reaction ◽  
Ambient Conditions ◽  
X Ray Diffraction ◽  
X Ray ◽  
Dicobalt Octacarbonyl

Dicobalt octacarbonyl reacts with (9-fluorenylidene)(2,2,6,6-tetramethylpiperidino)borane (1) at ambient conditions in an unexpected [2+2]-cycloaddition to yield an oxaboretane derivative (2). The structure of 2 has been determined by X-ray diffraction analysis. Similarities between the complex 2 and other oxaboretanes are discussed.

The crystal and molecular structure of 1,4-diphenyl-2,2′,3,3′,5,5′,6,6′-octamethylcyclo-1,4-diphospha-2,3,5,6-tetrasilahexane, a phosphorus–silicon heterocycle

1979 ◽  
Vol 57 (2) ◽  
pp. 174-179 ◽  
Author(s):  
A. Wallace Cordes ◽  
Paul F. Schubert ◽  
Richard T. Oakley
Keyword(s):  
Molecular Structure ◽  
Crystal And Molecular Structure ◽  
Direct Methods ◽  
Chair Conformation ◽  
Monoclinic Space Group ◽  
Single Bond ◽  
X Ray Diffraction ◽  
Full Matrix ◽  
X Ray ◽  
Bond Lengths

The crystal structure of 1,4-diphenyl-2,2′,3,3′,5,5′,6,6′-octamethylcyclo-1,4-diphospha-2,3,5,6-tetrasilahexane, (PhPSi2Me4)2, has been determined by single crystal X-ray diffraction. The crystals are monoclinic, space group P21/c, with a = 9.866(1), b = 11.921(1), and c = 11.324(2) Å, β = 104.31(1)°, Z = 2, and ρcalcd = 1.15 g/cm3. The structure was solved by direct methods and was refined by full-matrix least-squares procedures to a final R of 0.060 and Rw of 0.078, for 1173 reflections with intensities greater than 3σ. The (PhPSi2Me4)2 molecule lies on a crystallographic centre of symmetry, and the six-membered P2Si4 ring has a chair conformation with equatorial phenyl groups. The endocyclic angles at P (104.4(1)°) and Si (104.9(2)°) are intermediate between those found in cyclic hexaphosphine and hexasilane molecules, and the Si—Si and P—Si distances of 2.345(3) and 2.252(4) Å, respectively, correspond to single bond lengths, with no appreciable evidence for secondary pπ → dπ bonding between phosphorus and silicon. The Si—C (1.867(8) Å) and P—C (1.828(7) Å) bond lengths are also normal. The variations in the Si—P—C (101.6(2)°, 108.6(2)°), P—Si—C (range 106.2(3)–120.0(3)°), and Si—Si—C (range 105.8(3)–113.7(3)°) angles indicate that the positions of the exocyclic methyl and phenyl groups are influenced by both intra- and intermolecular steric forces.

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