Synthesis and Structures of (p-Halogenophenoxy)phosphazenes: Comparison of the Structures of Cyclic and Linear Short-Chain Species

Harry R. Allcock, Dennis C. Ngo, Masood Parvez, Karyn B. Visscher

Research output: Contribution to journalArticle

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Abstract

The crystal structures of OP(OR)2NP(OR)3, where OR = O-C6H4F-p, O-C6H4Cl-p, and O-C6H4Br-p, and [NP- (OR)2]3, where OR = O-C6H4F-p, O-C6H4Cl-p, O-C6H4Br-p and O-C6H4I-p, were determined by X-ray crystallography. These small molecule phosphazenes are structural models for the corresponding high polymers, and their structures provide insight into the conformation and nature of bonding in the polymeric species. Crystals of OP(O-C6H4F-p)2NP(O-C6H4F-p)3 are triclinic with cell dimensions of a = 8.394(2) Å, b = 10.690(3) Å, c = 16.760(4) Å, a = 86.99(2)°, β = 84.82(2)°, γ = 69.66(2)°, space group P[formula omitted], Z = 2. Crystals of OP(0-C6H4-Cl-p)2NP(O-C6H4Cl-p)3 are triclinic with cell dimension of a = 10.513(6) Å, b = 12.574(3) Å, c = 13.359(5) Å, α = 91.83(3)°, β = 106.76(4)°, γ = 104.68(3)°, space group. and Z = 2. Crystals of OP(O-C6H4Br-p)2NP-(O-C6H4Br-p) are triclinic with cell dimension of a = 9.839(2) Å, b = 12.373(4) Å, c = 14.286(3) Å, α = 103.74(2)°, β = 91.76(2)°, γ = 100.89(2)°, space group P[formula omitted], and Z = 2. Crystals of the cyclic species are monoclinic. The unit cell dimensions are as follows: [NP(O-C6H4F-p)2] 3, a = 20.860(5) Å, b = 8.085(12) Å, c = 21.813(5) Å, β = 104.62(3)°, space group P21/n, Z = 4; [NP(O-C6H4Cl-p)2]3, a = 17.746(9) Å, b = 7.623(7) Å, c = 27.856(10) Å, β= 91.76(12)°, space group P21/c,Z = 4; [NP(O-C6H4Br-p)2]3, a = 13.680(5) Å, b = 31.316(7) Å, c = 9.289(3).β = 90.70(3)°, space group P21/n, Z = 4; [NP(O-C6H4I-p)2]3, a = 13.700(6) Å, b = 9.381(11) Å, c = 32.675(16) Å, β = 95.72(4)°, space group P21/c, Z = 4. The results show that the P-N bond lengths in both the short-chain and cyclic species are very similar, with an average value of 1.55 Å. Evidence for side group stacking can be detected in the crystal lattice of both the cyclic and linear oligomers, and these arrangements are analogous to those expected in polymer microcrystallites.

Original languageEnglish (US)
Pages (from-to)2090-2102
Number of pages13
JournalInorganic Chemistry
Volume33
Issue number10
DOIs
StatePublished - May 1 1994

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Crystals
synthesis
Polymers
X ray crystallography
Bond length
cells
Oligomers
Crystal lattices
crystals
Conformations
Crystal structure
high polymers
Molecules
oligomers
crystal lattices
crystallography
crystal structure
polymers
molecules
x rays

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

Cite this

@article{d228f9bf15264286af7b5e48bc1689c9,
title = "Synthesis and Structures of (p-Halogenophenoxy)phosphazenes: Comparison of the Structures of Cyclic and Linear Short-Chain Species",
abstract = "The crystal structures of OP(OR)2NP(OR)3, where OR = O-C6H4F-p, O-C6H4Cl-p, and O-C6H4Br-p, and [NP- (OR)2]3, where OR = O-C6H4F-p, O-C6H4Cl-p, O-C6H4Br-p and O-C6H4I-p, were determined by X-ray crystallography. These small molecule phosphazenes are structural models for the corresponding high polymers, and their structures provide insight into the conformation and nature of bonding in the polymeric species. Crystals of OP(O-C6H4F-p)2NP(O-C6H4F-p)3 are triclinic with cell dimensions of a = 8.394(2) {\AA}, b = 10.690(3) {\AA}, c = 16.760(4) {\AA}, a = 86.99(2)°, β = 84.82(2)°, γ = 69.66(2)°, space group P[formula omitted], Z = 2. Crystals of OP(0-C6H4-Cl-p)2NP(O-C6H4Cl-p)3 are triclinic with cell dimension of a = 10.513(6) {\AA}, b = 12.574(3) {\AA}, c = 13.359(5) {\AA}, α = 91.83(3)°, β = 106.76(4)°, γ = 104.68(3)°, space group. and Z = 2. Crystals of OP(O-C6H4Br-p)2NP-(O-C6H4Br-p) are triclinic with cell dimension of a = 9.839(2) {\AA}, b = 12.373(4) {\AA}, c = 14.286(3) {\AA}, α = 103.74(2)°, β = 91.76(2)°, γ = 100.89(2)°, space group P[formula omitted], and Z = 2. Crystals of the cyclic species are monoclinic. The unit cell dimensions are as follows: [NP(O-C6H4F-p)2] 3, a = 20.860(5) {\AA}, b = 8.085(12) {\AA}, c = 21.813(5) {\AA}, β = 104.62(3)°, space group P21/n, Z = 4; [NP(O-C6H4Cl-p)2]3, a = 17.746(9) {\AA}, b = 7.623(7) {\AA}, c = 27.856(10) {\AA}, β= 91.76(12)°, space group P21/c,Z = 4; [NP(O-C6H4Br-p)2]3, a = 13.680(5) {\AA}, b = 31.316(7) {\AA}, c = 9.289(3).β = 90.70(3)°, space group P21/n, Z = 4; [NP(O-C6H4I-p)2]3, a = 13.700(6) {\AA}, b = 9.381(11) {\AA}, c = 32.675(16) {\AA}, β = 95.72(4)°, space group P21/c, Z = 4. The results show that the P-N bond lengths in both the short-chain and cyclic species are very similar, with an average value of 1.55 {\AA}. Evidence for side group stacking can be detected in the crystal lattice of both the cyclic and linear oligomers, and these arrangements are analogous to those expected in polymer microcrystallites.",
author = "Allcock, {Harry R.} and Ngo, {Dennis C.} and Masood Parvez and Visscher, {Karyn B.}",
year = "1994",
month = "5",
day = "1",
doi = "10.1021/ic00088a008",
language = "English (US)",
volume = "33",
pages = "2090--2102",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "10",

}

Synthesis and Structures of (p-Halogenophenoxy)phosphazenes : Comparison of the Structures of Cyclic and Linear Short-Chain Species. / Allcock, Harry R.; Ngo, Dennis C.; Parvez, Masood; Visscher, Karyn B.

In: Inorganic Chemistry, Vol. 33, No. 10, 01.05.1994, p. 2090-2102.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis and Structures of (p-Halogenophenoxy)phosphazenes

T2 - Comparison of the Structures of Cyclic and Linear Short-Chain Species

AU - Allcock, Harry R.

AU - Ngo, Dennis C.

AU - Parvez, Masood

AU - Visscher, Karyn B.

PY - 1994/5/1

Y1 - 1994/5/1

N2 - The crystal structures of OP(OR)2NP(OR)3, where OR = O-C6H4F-p, O-C6H4Cl-p, and O-C6H4Br-p, and [NP- (OR)2]3, where OR = O-C6H4F-p, O-C6H4Cl-p, O-C6H4Br-p and O-C6H4I-p, were determined by X-ray crystallography. These small molecule phosphazenes are structural models for the corresponding high polymers, and their structures provide insight into the conformation and nature of bonding in the polymeric species. Crystals of OP(O-C6H4F-p)2NP(O-C6H4F-p)3 are triclinic with cell dimensions of a = 8.394(2) Å, b = 10.690(3) Å, c = 16.760(4) Å, a = 86.99(2)°, β = 84.82(2)°, γ = 69.66(2)°, space group P[formula omitted], Z = 2. Crystals of OP(0-C6H4-Cl-p)2NP(O-C6H4Cl-p)3 are triclinic with cell dimension of a = 10.513(6) Å, b = 12.574(3) Å, c = 13.359(5) Å, α = 91.83(3)°, β = 106.76(4)°, γ = 104.68(3)°, space group. and Z = 2. Crystals of OP(O-C6H4Br-p)2NP-(O-C6H4Br-p) are triclinic with cell dimension of a = 9.839(2) Å, b = 12.373(4) Å, c = 14.286(3) Å, α = 103.74(2)°, β = 91.76(2)°, γ = 100.89(2)°, space group P[formula omitted], and Z = 2. Crystals of the cyclic species are monoclinic. The unit cell dimensions are as follows: [NP(O-C6H4F-p)2] 3, a = 20.860(5) Å, b = 8.085(12) Å, c = 21.813(5) Å, β = 104.62(3)°, space group P21/n, Z = 4; [NP(O-C6H4Cl-p)2]3, a = 17.746(9) Å, b = 7.623(7) Å, c = 27.856(10) Å, β= 91.76(12)°, space group P21/c,Z = 4; [NP(O-C6H4Br-p)2]3, a = 13.680(5) Å, b = 31.316(7) Å, c = 9.289(3).β = 90.70(3)°, space group P21/n, Z = 4; [NP(O-C6H4I-p)2]3, a = 13.700(6) Å, b = 9.381(11) Å, c = 32.675(16) Å, β = 95.72(4)°, space group P21/c, Z = 4. The results show that the P-N bond lengths in both the short-chain and cyclic species are very similar, with an average value of 1.55 Å. Evidence for side group stacking can be detected in the crystal lattice of both the cyclic and linear oligomers, and these arrangements are analogous to those expected in polymer microcrystallites.

AB - The crystal structures of OP(OR)2NP(OR)3, where OR = O-C6H4F-p, O-C6H4Cl-p, and O-C6H4Br-p, and [NP- (OR)2]3, where OR = O-C6H4F-p, O-C6H4Cl-p, O-C6H4Br-p and O-C6H4I-p, were determined by X-ray crystallography. These small molecule phosphazenes are structural models for the corresponding high polymers, and their structures provide insight into the conformation and nature of bonding in the polymeric species. Crystals of OP(O-C6H4F-p)2NP(O-C6H4F-p)3 are triclinic with cell dimensions of a = 8.394(2) Å, b = 10.690(3) Å, c = 16.760(4) Å, a = 86.99(2)°, β = 84.82(2)°, γ = 69.66(2)°, space group P[formula omitted], Z = 2. Crystals of OP(0-C6H4-Cl-p)2NP(O-C6H4Cl-p)3 are triclinic with cell dimension of a = 10.513(6) Å, b = 12.574(3) Å, c = 13.359(5) Å, α = 91.83(3)°, β = 106.76(4)°, γ = 104.68(3)°, space group. and Z = 2. Crystals of OP(O-C6H4Br-p)2NP-(O-C6H4Br-p) are triclinic with cell dimension of a = 9.839(2) Å, b = 12.373(4) Å, c = 14.286(3) Å, α = 103.74(2)°, β = 91.76(2)°, γ = 100.89(2)°, space group P[formula omitted], and Z = 2. Crystals of the cyclic species are monoclinic. The unit cell dimensions are as follows: [NP(O-C6H4F-p)2] 3, a = 20.860(5) Å, b = 8.085(12) Å, c = 21.813(5) Å, β = 104.62(3)°, space group P21/n, Z = 4; [NP(O-C6H4Cl-p)2]3, a = 17.746(9) Å, b = 7.623(7) Å, c = 27.856(10) Å, β= 91.76(12)°, space group P21/c,Z = 4; [NP(O-C6H4Br-p)2]3, a = 13.680(5) Å, b = 31.316(7) Å, c = 9.289(3).β = 90.70(3)°, space group P21/n, Z = 4; [NP(O-C6H4I-p)2]3, a = 13.700(6) Å, b = 9.381(11) Å, c = 32.675(16) Å, β = 95.72(4)°, space group P21/c, Z = 4. The results show that the P-N bond lengths in both the short-chain and cyclic species are very similar, with an average value of 1.55 Å. Evidence for side group stacking can be detected in the crystal lattice of both the cyclic and linear oligomers, and these arrangements are analogous to those expected in polymer microcrystallites.

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