Coordination chemistry of alkali and alkaline earth cations

Synthesis and X-ray crystal structure of cesium (picrate) (benzo-15-crown-5) Cs+C6H2N3O7 -(C14H20O5)

K. Venkatasubramanian, K. Joshi, N. S. Poonia, William "Bill" Montfort, S. R. Ernst, M. L. Hackert

Research output: Contribution to journalArticle

15 Citations (Scopus)

Abstract

Crystals of the Cs+ Pic- (B15C5) complex (Pic=picrate; B15C5=benzo-15-crown-5) (Mr=629.3) are yellow prisms which belong to the triclinic space group Pī with a=7.377(4), b=11.372(2), c=14.806(2) Å, α=90.31(1), β=91.06(2), γ=108.32(2)0, Z=2, Dx=1.77, and Dm=1.77 g cm-3. Final R=0.055 for 3575 observed reflections out of a total of 4004 measured reflections. Cesium forms a 1:1 anion paired complex with B15C5 like sodium rather than a charge separated sandwich structure as found for potassium and expected for cesium in view of the ion-cavity radius concept. The Cs cation is 9-coordinate involving the five crown oxygens (Cs...O, 3.00(1) to 3.24(1) Å), the phenoxide (Cs...O-, 3.03(1) Å) and an ortho nitro group oxygen (Cs...O, 3.01(1) Å) of the picrate counteranion and, uniquely, with two additional oxygens (Cs...O, 3.17(1) and 3.40(1) Å) from a para nitro group of the picrate belonging to the adjacent molecule in the lattice. The Cs+ ion lies 2.07 Å out of the mean plane formed by the crown oxygens. This system provides the first structural evidence that the interaction stoichiometry of an alkali cation with a cyclic multidentate ligand is not a function of the ion and cavity size alone but also of its Lewis acid strength as modified by the charge neutralizing anion.

Original languageEnglish (US)
Pages (from-to)453-459
Number of pages7
JournalJournal of Inclusion Phenomena
Volume3
Issue number4
DOIs
StatePublished - Dec 1985
Externally publishedYes

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picrates
Cesium
cesium
Alkalies
crystal structure
alkalis
Cations
alkalies
cations
chemistry
X-radiation
Crystal structure
Earth (planet)
X-Rays
Oxygen
oxygen
X rays
synthesis
Ions
ions

Keywords

  • benzo-15-crown-5
  • cesium ion
  • picrate ion
  • X-ray structural analysis

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Chemistry(all)

Cite this

Coordination chemistry of alkali and alkaline earth cations : Synthesis and X-ray crystal structure of cesium (picrate) (benzo-15-crown-5) Cs+C6H2N3O7 -(C14H20O5). / Venkatasubramanian, K.; Joshi, K.; Poonia, N. S.; Montfort, William "Bill"; Ernst, S. R.; Hackert, M. L.

In: Journal of Inclusion Phenomena, Vol. 3, No. 4, 12.1985, p. 453-459.

Research output: Contribution to journalArticle

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abstract = "Crystals of the Cs+ Pic- (B15C5) complex (Pic=picrate; B15C5=benzo-15-crown-5) (Mr=629.3) are yellow prisms which belong to the triclinic space group Pī with a=7.377(4), b=11.372(2), c=14.806(2) {\AA}, α=90.31(1), β=91.06(2), γ=108.32(2)0, Z=2, Dx=1.77, and Dm=1.77 g cm-3. Final R=0.055 for 3575 observed reflections out of a total of 4004 measured reflections. Cesium forms a 1:1 anion paired complex with B15C5 like sodium rather than a charge separated sandwich structure as found for potassium and expected for cesium in view of the ion-cavity radius concept. The Cs cation is 9-coordinate involving the five crown oxygens (Cs...O, 3.00(1) to 3.24(1) {\AA}), the phenoxide (Cs...O-, 3.03(1) {\AA}) and an ortho nitro group oxygen (Cs...O, 3.01(1) {\AA}) of the picrate counteranion and, uniquely, with two additional oxygens (Cs...O, 3.17(1) and 3.40(1) {\AA}) from a para nitro group of the picrate belonging to the adjacent molecule in the lattice. The Cs+ ion lies 2.07 {\AA} out of the mean plane formed by the crown oxygens. This system provides the first structural evidence that the interaction stoichiometry of an alkali cation with a cyclic multidentate ligand is not a function of the ion and cavity size alone but also of its Lewis acid strength as modified by the charge neutralizing anion.",
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T2 - Synthesis and X-ray crystal structure of cesium (picrate) (benzo-15-crown-5) Cs+C6H2N3O7 -(C14H20O5)

AU - Venkatasubramanian, K.

AU - Joshi, K.

AU - Poonia, N. S.

AU - Montfort, William "Bill"

AU - Ernst, S. R.

AU - Hackert, M. L.

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AB - Crystals of the Cs+ Pic- (B15C5) complex (Pic=picrate; B15C5=benzo-15-crown-5) (Mr=629.3) are yellow prisms which belong to the triclinic space group Pī with a=7.377(4), b=11.372(2), c=14.806(2) Å, α=90.31(1), β=91.06(2), γ=108.32(2)0, Z=2, Dx=1.77, and Dm=1.77 g cm-3. Final R=0.055 for 3575 observed reflections out of a total of 4004 measured reflections. Cesium forms a 1:1 anion paired complex with B15C5 like sodium rather than a charge separated sandwich structure as found for potassium and expected for cesium in view of the ion-cavity radius concept. The Cs cation is 9-coordinate involving the five crown oxygens (Cs...O, 3.00(1) to 3.24(1) Å), the phenoxide (Cs...O-, 3.03(1) Å) and an ortho nitro group oxygen (Cs...O, 3.01(1) Å) of the picrate counteranion and, uniquely, with two additional oxygens (Cs...O, 3.17(1) and 3.40(1) Å) from a para nitro group of the picrate belonging to the adjacent molecule in the lattice. The Cs+ ion lies 2.07 Å out of the mean plane formed by the crown oxygens. This system provides the first structural evidence that the interaction stoichiometry of an alkali cation with a cyclic multidentate ligand is not a function of the ion and cavity size alone but also of its Lewis acid strength as modified by the charge neutralizing anion.

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KW - X-ray structural analysis

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