skip to main content
US FlagAn official website of the United States government
dot gov icon
Official websites use .gov
A .gov website belongs to an official government organization in the United States.
https lock icon
Secure .gov websites use HTTPS
A lock ( lock ) or https:// means you've safely connected to the .gov website. Share sensitive information only on official, secure websites.


Title: Crystal structures of trans -acetyldicarbonyl(η 5 -cyclopentadienyl)(1,3,5-triaza-7-phosphaadamantane)molybdenum(II) and trans -acetyldicarbonyl(η 5 -cyclopentadienyl)(3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane)molybdenum(II)
The title compounds, [Mo(C 5 H 5 )(COCH 3 )(C 6 H 12 N 3 P)(CO) 2 ], (1), and [Mo(C 5 H 5 )(COCH 3 )(C 9 H 16 N 3 O 2 P)(C 6 H 5 ) 2 ))(CO) 2 ], (2), have been prepared by phosphine-induced migratory insertion from [Mo(C 5 H 5 )(CO) 3 (CH 3 )]. The molecular structures of these complexes are quite similar, exhibiting a four-legged piano-stool geometry with trans -disposed carbonyl ligands. The extended structures of complexes (1) and (2) differ substantially. For complex (1), the molybdenum acetyl unit plays a dominant role in the organization of the extended structure, joining the molecules into centrosymmetrical dimers through C—H...O interactions with a cyclopentadienyl ligand of a neighboring molecule, and these dimers are linked into layers parallel to (100) by C—H...O interactions between the molybdenum acetyl and the cyclopentadienyl ligand of another neighbor. The extended structure of (2) is dominated by C—H...O interactions involving the carbonyl groups of the acetamide groups of the DAPTA ligand, which join the molecules into centrosymmetrical dimers and link them into chains along [010]. Additional C—H...O interactions between the molybdenum acetyl oxygen atom and an acetamide methyl group join the chains into layers parallel to (101).  more » « less
Award ID(s):
1552591
PAR ID:
10237179
Author(s) / Creator(s):
; ; ; ;
Date Published:
Journal Name:
Acta Crystallographica Section E Crystallographic Communications
Volume:
76
Issue:
4
ISSN:
2056-9890
Page Range / eLocation ID:
547 to 551
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. The title compound, [Mo(C 5 H 5 )(C 2 H 3 O)(C 24 H 27 P)(CO) 2 ], was prepared by reaction of [Mo(C 5 H 5 )(CO) 3 (CH 3 )] with tris(3,5-dimethylphenyl)phosphane. The complex exhibits a four-legged piano-stool geometry with trans -disposed acetyl and phosphane ligands. The molecular geometry is nearly identical to that of the triphenylphosphane derivative, but introduction of methyl groups on the aromatic phosphane substituents significantly impacts supramolecular organization. In the crystal, non-classical C—H...O interactions involving the acetyl carbonyl group lead to a chain motif along [010], and another set of C—H...O close contacts join inversion-related molecules. 
    more » « less
  2. Three cyclopentadienylmolybdenum(II) propionyl complexes featuring triarylphosphine ligands with different para substituents, namely, dicarbonyl(η 5 -cyclopentadienyl)propionyl(triphenylphosphane-κ P )molybdenum(II), [Mo(C 5 H 5 )(C 3 H 5 O)(C 18 H 15 P)(CO) 2 ], ( 1 ), dicarbonyl(η 5 -cyclopentadienyl)propionyl[tris(4-fluorophenyl)phosphane-κ P ]molybdenum(II), [Mo(C 5 H 5 )(C 3 H 5 O)(C 18 H 12 F 3 P)(CO) 2 ], ( 2 ), and dicarbonyl(η 5 -cyclopentadienyl)propionyl[tris(4-methoxyphenyl)phosphane-κ P ]molybdenum(II) dichloromethane solvate, [Mo(C 5 H 5 )(C 3 H 5 O)(C 21 H 21 O 3 P)(CO) 2 ]·CH 2 Cl 2 , ( 3 ), have been prepared from the corresponding ethyl complexes via phosphine-induced migratory insertion. These complexes exhibit four-legged piano-stool geometries with molecular structures quite similar to each other and to related acetyl complexes. The extended structures of the three complexes differ somewhat, with the para substituent of the triarylphosphine of ( 2 ) (fluoro) or ( 3 ) (methoxy) engaging in non-classical C—H...F or C—H...O hydrogen-bonding interactions. The structure of ( 3 ) exhibits modest disorder in the position of one Cl atom of the dichloromethane solvent, which was modeled with two sites showing approximately equivalent occupancies [0.532 (15) and 0.478 (15)]. 
    more » « less
  3. null (Ed.)
    The green compound poly[(tetrahydrofuran)tris[μ-η 5 :η 5 -1-(trimethylsilyl)cyclopentadienyl]caesium(I)ytterbium(II)], [CsYb(C 8 H 13 Si) 3 (C 4 H 8 O)] n or [(THF)Cs(μ-η 5 :η 5 -Cp′) 3 Yb II ] n was synthesized by reduction of a red THF solution of (C 5 H 4 SiMe 3 ) 3 Yb III with excess Cs metal and identified by X-ray diffraction. The compound crystallizes as a two-dimensional array of hexagons with alternating Cs I and Yb II ions at the vertices and cyclopentadienyl groups bridging each edge. This, based off the six-electron cyclopentadienyl rings occupying three coordination positions, gives a formally nine-coordinate tris(cyclopentadienyl) coordination environment to Yb and the Cs is ten-coordinate due to the three cyclopentadienyl rings and a coordinated molecule of THF. The complex comprises layers of Cs 3 Yb 3 hexagons with THF ligands and Me 3 Si groups in between the layers. The Yb—C metrical parameters are consistent with a 4 f 14 Yb II electron configuration. 
    more » « less
  4. The title complex, (1,4,7,10,13,16-hexaoxacyclooctadecane-1κ6O)(μ-oxalato-1κ2O1,O2:2κ2O1′,O2′)triphenyl-2κ3C-potassium(I)tin(IV), [KSn(C6H5)3(C2O4)(C12H24O6)] or K[18-Crown-6][(C6H5)3SnO4C2], was synthesized. The complex consists of a potassium cation coordinated to the six oxygen atoms of a crown ether molecule and the two oxygen atoms of the oxalatotriphenylstannate anion. It crystallizes in the monoclinic crystal system within the space groupP21. The tin atom is coordinated by one chelating oxalate ligand and three phenyl groups, forming acis-trigonal–bipyramidal geometry around the tin atom. The cations and anions form ion pairs, linked through carbonyl coordination to the potassium atoms. The crystal structure features C—H...O hydrogen bonds between the oxygen atoms of the oxalate group and the hydrogen atoms of the phenyl groups, resulting in an infinite chain structure extending alonga-axis direction. The primary inter-chain interactions are van der Waals forces. 
    more » « less
  5. In the title compound, C10H12N2O4, the four substituents lie out of the phenyl plane by varying degrees. The methyl C atom lies 0.019 (3) A ˚ out of plane, while the methoxy O and C atoms lie 0.067 (2) and 0.042 (3) A ˚ out of plane, respectively, with the C—C—O—C torsion angle being 3.3 (2). The plane of the nitro group is twisted out of the phenyl plane, forming a dihedral angle of 12.03 (9) with it. The acetamide substituent is twisted considerably more out of the phenyl plane, forming a dihedral angle of 47.24 (6) with it. In the extended structure, the acetamide NH group donates a hydrogen bond to an acetamide carbonyl O atom, thereby forming chains propagating in the [010] direction. 
    more » « less