Structures and related properties of AgX bearing 3,3′-thiobispyridine (X- = NO3 -, BF4 -, ClO4 -, and PF6 -)

O. S. Jung, Y. J. Kim, Y. A. Lee, H. K. Chae, Ho Gyeom Jang, J. Hong

Research output: Contribution to journalArticle

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Abstract

Infinite molecular helices [Ag(3,3′-Py2S)]X (3,3′-Py2S = 3,3′-thiobispyridine; X- = BF4 -, ClO4 -, and PF6 -) have been rationally constructed or induced. Crystallographic characterization (X- = BF4 -, monoclinic P21/n, a = 8.946(3) Å, b = 14.130(2) Å, c = 10.124(2) Å, β = 107.83(2)°, V = 1218.3(5) Å3, Z = 4, R = 0.0351; X- = ClO4 -, monoclinic P21/n, a = 8.884(1) Å, b = 14.305(3) Å, c = 10.110(1) Å, β = 106.78(1)°, V = 1230.1(3) Å3, Z = 4, R = 0.0417; X- = PF6 -, monoclinic P21/c, a = 10.959(2) Å, b = 9.808(2) Å, c = 14.065(3) Å, β = 112.03(2)°, V = 1401.4(5) Å3, Z = 4, R = 0.0442) reveals that the skeletal structure is an oblong cylindrical cationic helix consisting of alternating Ag(I) and 3,3′-Py2S species and that its counteranions are pinched in two columns inside each helix. The formation of the helical coordination polymer appears to be primarily associated with a suitable combination of the skewed conformer of 3,3′-Py2S and the potential linear geometry of the N-Ag(I)-N bond. However, the framework of the nitrate analogue [Ag(3,3′-Py2S)NO3] (monoclinic P21/c, a = 8.177(2) Å, b = 10.291(1) Å, c = 14.771(2) Å, β = 102.19(1)°, V = 1214.9(4) Å3, Z = 4, R = 0.0300) is a two-dimensional network consisting of an 18-membered ring unit, where each 3,3′-Py2S acts as a N,N′,S- tridentate ligand connecting three tetrahedral silver(I) ions with the monodentate nitrate weakly bonded to the silver (Ag···O = 2.65(1) Å) rather than acting as a counteranion. The anion exchange of [Ag(3,3′-Py2S)-NO3] with BF4 -, ClO4 -, or PF6 - has been accomplished in aqueous media. The two-dimensional networks are easily converted into the helices via the anion exchange, but the reverse anion exchange proceeds slightly. Thermal analyses indicate a relationship between the thermal stabilities and the structural properties.

Original languageEnglish
Pages (from-to)2105-2110
Number of pages6
JournalInorganic Chemistry
Volume40
Issue number9
DOIs
Publication statusPublished - 2001 Apr 23

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Bearings (structural)
helices
Anions
Silver
Nitrates
Hot Temperature
anions
nitrates
silver
Structural properties
Polymers
Thermodynamic stability
coordination polymers
Ions
Ligands
thermal stability
Geometry
analogs
ligands
perchlorate

ASJC Scopus subject areas

  • Inorganic Chemistry

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Structures and related properties of AgX bearing 3,3′-thiobispyridine (X- = NO3 -, BF4 -, ClO4 -, and PF6 -). / Jung, O. S.; Kim, Y. J.; Lee, Y. A.; Chae, H. K.; Jang, Ho Gyeom; Hong, J.

In: Inorganic Chemistry, Vol. 40, No. 9, 23.04.2001, p. 2105-2110.

Research output: Contribution to journalArticle

Jung, O. S. ; Kim, Y. J. ; Lee, Y. A. ; Chae, H. K. ; Jang, Ho Gyeom ; Hong, J. / Structures and related properties of AgX bearing 3,3′-thiobispyridine (X- = NO3 -, BF4 -, ClO4 -, and PF6 -). In: Inorganic Chemistry. 2001 ; Vol. 40, No. 9. pp. 2105-2110.
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title = "Structures and related properties of AgX bearing 3,3′-thiobispyridine (X- = NO3 -, BF4 -, ClO4 -, and PF6 -)",
abstract = "Infinite molecular helices [Ag(3,3′-Py2S)]X (3,3′-Py2S = 3,3′-thiobispyridine; X- = BF4 -, ClO4 -, and PF6 -) have been rationally constructed or induced. Crystallographic characterization (X- = BF4 -, monoclinic P21/n, a = 8.946(3) {\AA}, b = 14.130(2) {\AA}, c = 10.124(2) {\AA}, β = 107.83(2)°, V = 1218.3(5) {\AA}3, Z = 4, R = 0.0351; X- = ClO4 -, monoclinic P21/n, a = 8.884(1) {\AA}, b = 14.305(3) {\AA}, c = 10.110(1) {\AA}, β = 106.78(1)°, V = 1230.1(3) {\AA}3, Z = 4, R = 0.0417; X- = PF6 -, monoclinic P21/c, a = 10.959(2) {\AA}, b = 9.808(2) {\AA}, c = 14.065(3) {\AA}, β = 112.03(2)°, V = 1401.4(5) {\AA}3, Z = 4, R = 0.0442) reveals that the skeletal structure is an oblong cylindrical cationic helix consisting of alternating Ag(I) and 3,3′-Py2S species and that its counteranions are pinched in two columns inside each helix. The formation of the helical coordination polymer appears to be primarily associated with a suitable combination of the skewed conformer of 3,3′-Py2S and the potential linear geometry of the N-Ag(I)-N bond. However, the framework of the nitrate analogue [Ag(3,3′-Py2S)NO3] (monoclinic P21/c, a = 8.177(2) {\AA}, b = 10.291(1) {\AA}, c = 14.771(2) {\AA}, β = 102.19(1)°, V = 1214.9(4) {\AA}3, Z = 4, R = 0.0300) is a two-dimensional network consisting of an 18-membered ring unit, where each 3,3′-Py2S acts as a N,N′,S- tridentate ligand connecting three tetrahedral silver(I) ions with the monodentate nitrate weakly bonded to the silver (Ag···O = 2.65(1) {\AA}) rather than acting as a counteranion. The anion exchange of [Ag(3,3′-Py2S)-NO3] with BF4 -, ClO4 -, or PF6 - has been accomplished in aqueous media. The two-dimensional networks are easily converted into the helices via the anion exchange, but the reverse anion exchange proceeds slightly. Thermal analyses indicate a relationship between the thermal stabilities and the structural properties.",
author = "Jung, {O. S.} and Kim, {Y. J.} and Lee, {Y. A.} and Chae, {H. K.} and Jang, {Ho Gyeom} and J. Hong",
year = "2001",
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TY - JOUR

T1 - Structures and related properties of AgX bearing 3,3′-thiobispyridine (X- = NO3 -, BF4 -, ClO4 -, and PF6 -)

AU - Jung, O. S.

AU - Kim, Y. J.

AU - Lee, Y. A.

AU - Chae, H. K.

AU - Jang, Ho Gyeom

AU - Hong, J.

PY - 2001/4/23

Y1 - 2001/4/23

N2 - Infinite molecular helices [Ag(3,3′-Py2S)]X (3,3′-Py2S = 3,3′-thiobispyridine; X- = BF4 -, ClO4 -, and PF6 -) have been rationally constructed or induced. Crystallographic characterization (X- = BF4 -, monoclinic P21/n, a = 8.946(3) Å, b = 14.130(2) Å, c = 10.124(2) Å, β = 107.83(2)°, V = 1218.3(5) Å3, Z = 4, R = 0.0351; X- = ClO4 -, monoclinic P21/n, a = 8.884(1) Å, b = 14.305(3) Å, c = 10.110(1) Å, β = 106.78(1)°, V = 1230.1(3) Å3, Z = 4, R = 0.0417; X- = PF6 -, monoclinic P21/c, a = 10.959(2) Å, b = 9.808(2) Å, c = 14.065(3) Å, β = 112.03(2)°, V = 1401.4(5) Å3, Z = 4, R = 0.0442) reveals that the skeletal structure is an oblong cylindrical cationic helix consisting of alternating Ag(I) and 3,3′-Py2S species and that its counteranions are pinched in two columns inside each helix. The formation of the helical coordination polymer appears to be primarily associated with a suitable combination of the skewed conformer of 3,3′-Py2S and the potential linear geometry of the N-Ag(I)-N bond. However, the framework of the nitrate analogue [Ag(3,3′-Py2S)NO3] (monoclinic P21/c, a = 8.177(2) Å, b = 10.291(1) Å, c = 14.771(2) Å, β = 102.19(1)°, V = 1214.9(4) Å3, Z = 4, R = 0.0300) is a two-dimensional network consisting of an 18-membered ring unit, where each 3,3′-Py2S acts as a N,N′,S- tridentate ligand connecting three tetrahedral silver(I) ions with the monodentate nitrate weakly bonded to the silver (Ag···O = 2.65(1) Å) rather than acting as a counteranion. The anion exchange of [Ag(3,3′-Py2S)-NO3] with BF4 -, ClO4 -, or PF6 - has been accomplished in aqueous media. The two-dimensional networks are easily converted into the helices via the anion exchange, but the reverse anion exchange proceeds slightly. Thermal analyses indicate a relationship between the thermal stabilities and the structural properties.

AB - Infinite molecular helices [Ag(3,3′-Py2S)]X (3,3′-Py2S = 3,3′-thiobispyridine; X- = BF4 -, ClO4 -, and PF6 -) have been rationally constructed or induced. Crystallographic characterization (X- = BF4 -, monoclinic P21/n, a = 8.946(3) Å, b = 14.130(2) Å, c = 10.124(2) Å, β = 107.83(2)°, V = 1218.3(5) Å3, Z = 4, R = 0.0351; X- = ClO4 -, monoclinic P21/n, a = 8.884(1) Å, b = 14.305(3) Å, c = 10.110(1) Å, β = 106.78(1)°, V = 1230.1(3) Å3, Z = 4, R = 0.0417; X- = PF6 -, monoclinic P21/c, a = 10.959(2) Å, b = 9.808(2) Å, c = 14.065(3) Å, β = 112.03(2)°, V = 1401.4(5) Å3, Z = 4, R = 0.0442) reveals that the skeletal structure is an oblong cylindrical cationic helix consisting of alternating Ag(I) and 3,3′-Py2S species and that its counteranions are pinched in two columns inside each helix. The formation of the helical coordination polymer appears to be primarily associated with a suitable combination of the skewed conformer of 3,3′-Py2S and the potential linear geometry of the N-Ag(I)-N bond. However, the framework of the nitrate analogue [Ag(3,3′-Py2S)NO3] (monoclinic P21/c, a = 8.177(2) Å, b = 10.291(1) Å, c = 14.771(2) Å, β = 102.19(1)°, V = 1214.9(4) Å3, Z = 4, R = 0.0300) is a two-dimensional network consisting of an 18-membered ring unit, where each 3,3′-Py2S acts as a N,N′,S- tridentate ligand connecting three tetrahedral silver(I) ions with the monodentate nitrate weakly bonded to the silver (Ag···O = 2.65(1) Å) rather than acting as a counteranion. The anion exchange of [Ag(3,3′-Py2S)-NO3] with BF4 -, ClO4 -, or PF6 - has been accomplished in aqueous media. The two-dimensional networks are easily converted into the helices via the anion exchange, but the reverse anion exchange proceeds slightly. Thermal analyses indicate a relationship between the thermal stabilities and the structural properties.

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