Crystal structures of three hexakis(fluoroaryloxy)cyclotriphosphazenes

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Abstract

The syntheses and crystal structures of three cyclotriphosphazenes, all with fluorinated aryloxy side groups that generate different steric characteristics, viz. hexakis(pentafluorophenoxy)cyclotriphosphazene, N3P3(OC6F5)6, 1, hexakis[4-(trifluoromethyl)phenoxy]cyclotriphosphazene, N3P3[OC6H4(CF3)]6, 2 and hexakis[3,5-bis(trifluoromethyl)phenoxy]cyclotriphosphazene, N3P3[OC6H3(CF3)2]6 3, are reported. Specifically, each phosphorus atom bears either two pentafluorophenoxy, 4-trifluoromethylphenoxy, or 3,5-trifluoromethylphenoxy groups. The central six-membered phosphazene rings display envelope pucker conformations in each case, albeit to varying degrees. The maximum displacement of the 'flap atom' from the plane through the other ring atoms [0.308(5)Å] is seen in 1, in a molecule that is devoid of hydrogen atoms and which exhibits a 'wind-swept' look with all the aromatic rings displaced in the same direction. In 3 an intramolecular C - H(aromatic)⋯F interaction is observed. All the -CF3 groups in 2 and 3 exhibit positional disorder over two rotated orientations in close to statistical ratios. The extended structures of 2 and 3 are consolidated by C - H⋯F interactions of two kinds: (a) linear chains, and (b) cyclic between molecules related by inversion centers. In both 1 and 3, one of the six substituted phenyl rings has a parallel-displaced aromatic π-π stacking interaction with its respective symmetry mate with slippage values of 2.2Å in 1 and 1.0Å in 3. None of the structures reported here have solvent voids that could lead to clathrate formation.

Original languageEnglish (US)
Pages (from-to)1525-1530
Number of pages6
JournalActa Crystallographica Section E: Crystallographic Communications
Volume75
DOIs
StatePublished - Oct 1 2019

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Crystal structure
Atoms
crystal structure
rings
phosphazene
atoms
Molecules
clathrates
interactions
bears
Phosphorus
Conformations
phosphorus
molecules
voids
Hydrogen
hydrogen atoms
envelopes
disorders
inversions

All Science Journal Classification (ASJC) codes

  • Chemistry(all)
  • Materials Science(all)
  • Condensed Matter Physics

Cite this

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title = "Crystal structures of three hexakis(fluoroaryloxy)cyclotriphosphazenes",
abstract = "The syntheses and crystal structures of three cyclotriphosphazenes, all with fluorinated aryloxy side groups that generate different steric characteristics, viz. hexakis(pentafluorophenoxy)cyclotriphosphazene, N3P3(OC6F5)6, 1, hexakis[4-(trifluoromethyl)phenoxy]cyclotriphosphazene, N3P3[OC6H4(CF3)]6, 2 and hexakis[3,5-bis(trifluoromethyl)phenoxy]cyclotriphosphazene, N3P3[OC6H3(CF3)2]6 3, are reported. Specifically, each phosphorus atom bears either two pentafluorophenoxy, 4-trifluoromethylphenoxy, or 3,5-trifluoromethylphenoxy groups. The central six-membered phosphazene rings display envelope pucker conformations in each case, albeit to varying degrees. The maximum displacement of the 'flap atom' from the plane through the other ring atoms [0.308(5){\AA}] is seen in 1, in a molecule that is devoid of hydrogen atoms and which exhibits a 'wind-swept' look with all the aromatic rings displaced in the same direction. In 3 an intramolecular C - H(aromatic)⋯F interaction is observed. All the -CF3 groups in 2 and 3 exhibit positional disorder over two rotated orientations in close to statistical ratios. The extended structures of 2 and 3 are consolidated by C - H⋯F interactions of two kinds: (a) linear chains, and (b) cyclic between molecules related by inversion centers. In both 1 and 3, one of the six substituted phenyl rings has a parallel-displaced aromatic π-π stacking interaction with its respective symmetry mate with slippage values of 2.2{\AA} in 1 and 1.0{\AA} in 3. None of the structures reported here have solvent voids that could lead to clathrate formation.",
author = "Yennawar, {Hemant P.} and Hess, {Andrew R.} and Allcock, {Harry R.}",
year = "2019",
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T1 - Crystal structures of three hexakis(fluoroaryloxy)cyclotriphosphazenes

AU - Yennawar, Hemant P.

AU - Hess, Andrew R.

AU - Allcock, Harry R.

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N2 - The syntheses and crystal structures of three cyclotriphosphazenes, all with fluorinated aryloxy side groups that generate different steric characteristics, viz. hexakis(pentafluorophenoxy)cyclotriphosphazene, N3P3(OC6F5)6, 1, hexakis[4-(trifluoromethyl)phenoxy]cyclotriphosphazene, N3P3[OC6H4(CF3)]6, 2 and hexakis[3,5-bis(trifluoromethyl)phenoxy]cyclotriphosphazene, N3P3[OC6H3(CF3)2]6 3, are reported. Specifically, each phosphorus atom bears either two pentafluorophenoxy, 4-trifluoromethylphenoxy, or 3,5-trifluoromethylphenoxy groups. The central six-membered phosphazene rings display envelope pucker conformations in each case, albeit to varying degrees. The maximum displacement of the 'flap atom' from the plane through the other ring atoms [0.308(5)Å] is seen in 1, in a molecule that is devoid of hydrogen atoms and which exhibits a 'wind-swept' look with all the aromatic rings displaced in the same direction. In 3 an intramolecular C - H(aromatic)⋯F interaction is observed. All the -CF3 groups in 2 and 3 exhibit positional disorder over two rotated orientations in close to statistical ratios. The extended structures of 2 and 3 are consolidated by C - H⋯F interactions of two kinds: (a) linear chains, and (b) cyclic between molecules related by inversion centers. In both 1 and 3, one of the six substituted phenyl rings has a parallel-displaced aromatic π-π stacking interaction with its respective symmetry mate with slippage values of 2.2Å in 1 and 1.0Å in 3. None of the structures reported here have solvent voids that could lead to clathrate formation.

AB - The syntheses and crystal structures of three cyclotriphosphazenes, all with fluorinated aryloxy side groups that generate different steric characteristics, viz. hexakis(pentafluorophenoxy)cyclotriphosphazene, N3P3(OC6F5)6, 1, hexakis[4-(trifluoromethyl)phenoxy]cyclotriphosphazene, N3P3[OC6H4(CF3)]6, 2 and hexakis[3,5-bis(trifluoromethyl)phenoxy]cyclotriphosphazene, N3P3[OC6H3(CF3)2]6 3, are reported. Specifically, each phosphorus atom bears either two pentafluorophenoxy, 4-trifluoromethylphenoxy, or 3,5-trifluoromethylphenoxy groups. The central six-membered phosphazene rings display envelope pucker conformations in each case, albeit to varying degrees. The maximum displacement of the 'flap atom' from the plane through the other ring atoms [0.308(5)Å] is seen in 1, in a molecule that is devoid of hydrogen atoms and which exhibits a 'wind-swept' look with all the aromatic rings displaced in the same direction. In 3 an intramolecular C - H(aromatic)⋯F interaction is observed. All the -CF3 groups in 2 and 3 exhibit positional disorder over two rotated orientations in close to statistical ratios. The extended structures of 2 and 3 are consolidated by C - H⋯F interactions of two kinds: (a) linear chains, and (b) cyclic between molecules related by inversion centers. In both 1 and 3, one of the six substituted phenyl rings has a parallel-displaced aromatic π-π stacking interaction with its respective symmetry mate with slippage values of 2.2Å in 1 and 1.0Å in 3. None of the structures reported here have solvent voids that could lead to clathrate formation.

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