The effect of pH on the dimensionality of coordination polymers

L. Pan, T. Frydel, M. B. Sander, X. Huang, Jing Li

Research output: Contribution to journalArticle

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Abstract

Hydrothermal reactions of simple alkaline salts or their hydroxides with 3,5-pyrazoledicarboxylic acid (H3pdc) yielded seven new compounds. At a lower pH level three one-dimeinsional structures [Ca(Hpdc)(H2O)4]·2H2O (1), [Ca(Hpdc)(H2O)4]·H2O (2), and [Ba(H2pdc)2(H2O)4] ·2H2O (6) were obtained by evaporation of the solutions resulting from hydro(solvo)thermal reactions of MCl2 (M = Ca, Ba) with H3pdc in water (1, 6) or in water/Et3N (2) at 150 °C for 3 days. Crystal structures of 1 and 2 contain zigzag chains of metal centers bridged by a single Hpdc2- ligand, whereas structure 6 consists of linear chains of metal centers bridged by two H2pdc- ligands. A dimer molecule [Sr(H3pdc)(H2pdc)2 (H2O)3]2·2 (H3pdc)·4H2O (4) was obtained from a similar hydrothermal reaction using Sr(ClO4)2·6H2O instead of MCl2. This compound contains [2+2] metallomacrocycles: At higher pH levels (pH = 4-6), the three-dimensional polymers [M(Hpdc)(H2O)] (Ca 3, Sr 5, Ba 7) were isolated by reactions of MCl2 (M = Ca, Sr, Ba) with H3pdc in water/Et3N or in M(OH)2 (M = Ca, Sr, Ba) with H3pdc in water under hydro(solvo)thermal conditions (150 °C, 3 days). Calcium and strontium are seven- and nine-coordinated in 3 and 5, respectively; barium is nine- and ten-coordinated in 7. It was observed that the increase in pH resulted in a higher connectivity level of ligands, which in turn leads to a higher dimensionality of the crystal structures. The correlation between the structures and pH values will be discussed. Crystal data: for 1, monoclinic, space group P21/n (No. 14), with a = 8.382(2), b = 12.621(3), c = 11.767(2) Å, β = 98.91(3)°, Z = 4; for 2, 3, and 5, monoclinic, space group P21/c (No. 14), Z = 4, a = 7.711(2), b = 15.574(3), c = 9.341(2) Å, β = 96.73(3)°, Z = 4 (2), a = 6.616(1), b = 12.654(3), c = 8.782(2) Å, β = 103.65(3)°, Z = 4 (3), a = 9.213(2), b = 12.088(3), c = 6.196(2) Å, β = 98.96(3)° (5); for 4 and 7, triclinic, space group P (No. 2), with a = 11.263(2), b = 11.460(3), c = 12.904(2) Å, α = 71.54(3), β 98.96(3), γ = 89.03(3)°, Z = 1 (4), a = 7.107(1), b = 9.780(2), c = 11.431(2) Å, α = 74.69(3), β = 73.39(3), γ = 85.29(3)°, Z = 2 (7); for 6, monoclinic, space group C2/c (No. 15), with a = 20.493(4), b = 6.708(1), c = 15.939(3) Å, β = 123.56(3)°, Z = 4.

Original languageEnglish
Pages (from-to)1271-1283
Number of pages13
JournalInorganic Chemistry
Volume40
Issue number6
DOIs
Publication statusPublished - Mar 12 2001

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Hydroxides
coordination polymers
hydroxides
Polymers
acids
Water
Ligands
water
ligands
Crystal structure
Metals
Strontium
crystal structure
Barium
strontium
Dimers
metals
barium
3,5-pyrazoledicarboxylic acid
calcium

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

The effect of pH on the dimensionality of coordination polymers. / Pan, L.; Frydel, T.; Sander, M. B.; Huang, X.; Li, Jing.

In: Inorganic Chemistry, Vol. 40, No. 6, 12.03.2001, p. 1271-1283.

Research output: Contribution to journalArticle

Pan, L, Frydel, T, Sander, MB, Huang, X & Li, J 2001, 'The effect of pH on the dimensionality of coordination polymers', Inorganic Chemistry, vol. 40, no. 6, pp. 1271-1283. https://doi.org/10.1021/ic001012o
Pan, L. ; Frydel, T. ; Sander, M. B. ; Huang, X. ; Li, Jing. / The effect of pH on the dimensionality of coordination polymers. In: Inorganic Chemistry. 2001 ; Vol. 40, No. 6. pp. 1271-1283.
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title = "The effect of pH on the dimensionality of coordination polymers",
abstract = "Hydrothermal reactions of simple alkaline salts or their hydroxides with 3,5-pyrazoledicarboxylic acid (H3pdc) yielded seven new compounds. At a lower pH level three one-dimeinsional structures [Ca(Hpdc)(H2O)4]·2H2O (1), [Ca(Hpdc)(H2O)4]·H2O (2), and [Ba(H2pdc)2(H2O)4] ·2H2O (6) were obtained by evaporation of the solutions resulting from hydro(solvo)thermal reactions of MCl2 (M = Ca, Ba) with H3pdc in water (1, 6) or in water/Et3N (2) at 150 °C for 3 days. Crystal structures of 1 and 2 contain zigzag chains of metal centers bridged by a single Hpdc2- ligand, whereas structure 6 consists of linear chains of metal centers bridged by two H2pdc- ligands. A dimer molecule [Sr(H3pdc)(H2pdc)2 (H2O)3]2·2 (H3pdc)·4H2O (4) was obtained from a similar hydrothermal reaction using Sr(ClO4)2·6H2O instead of MCl2. This compound contains [2+2] metallomacrocycles: At higher pH levels (pH = 4-6), the three-dimensional polymers [M(Hpdc)(H2O)] (Ca 3, Sr 5, Ba 7) were isolated by reactions of MCl2 (M = Ca, Sr, Ba) with H3pdc in water/Et3N or in M(OH)2 (M = Ca, Sr, Ba) with H3pdc in water under hydro(solvo)thermal conditions (150 °C, 3 days). Calcium and strontium are seven- and nine-coordinated in 3 and 5, respectively; barium is nine- and ten-coordinated in 7. It was observed that the increase in pH resulted in a higher connectivity level of ligands, which in turn leads to a higher dimensionality of the crystal structures. The correlation between the structures and pH values will be discussed. Crystal data: for 1, monoclinic, space group P21/n (No. 14), with a = 8.382(2), b = 12.621(3), c = 11.767(2) {\AA}, β = 98.91(3)°, Z = 4; for 2, 3, and 5, monoclinic, space group P21/c (No. 14), Z = 4, a = 7.711(2), b = 15.574(3), c = 9.341(2) {\AA}, β = 96.73(3)°, Z = 4 (2), a = 6.616(1), b = 12.654(3), c = 8.782(2) {\AA}, β = 103.65(3)°, Z = 4 (3), a = 9.213(2), b = 12.088(3), c = 6.196(2) {\AA}, β = 98.96(3)° (5); for 4 and 7, triclinic, space group P (No. 2), with a = 11.263(2), b = 11.460(3), c = 12.904(2) {\AA}, α = 71.54(3), β 98.96(3), γ = 89.03(3)°, Z = 1 (4), a = 7.107(1), b = 9.780(2), c = 11.431(2) {\AA}, α = 74.69(3), β = 73.39(3), γ = 85.29(3)°, Z = 2 (7); for 6, monoclinic, space group C2/c (No. 15), with a = 20.493(4), b = 6.708(1), c = 15.939(3) {\AA}, β = 123.56(3)°, Z = 4.",
author = "L. Pan and T. Frydel and Sander, {M. B.} and X. Huang and Jing Li",
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TY - JOUR

T1 - The effect of pH on the dimensionality of coordination polymers

AU - Pan, L.

AU - Frydel, T.

AU - Sander, M. B.

AU - Huang, X.

AU - Li, Jing

PY - 2001/3/12

Y1 - 2001/3/12

N2 - Hydrothermal reactions of simple alkaline salts or their hydroxides with 3,5-pyrazoledicarboxylic acid (H3pdc) yielded seven new compounds. At a lower pH level three one-dimeinsional structures [Ca(Hpdc)(H2O)4]·2H2O (1), [Ca(Hpdc)(H2O)4]·H2O (2), and [Ba(H2pdc)2(H2O)4] ·2H2O (6) were obtained by evaporation of the solutions resulting from hydro(solvo)thermal reactions of MCl2 (M = Ca, Ba) with H3pdc in water (1, 6) or in water/Et3N (2) at 150 °C for 3 days. Crystal structures of 1 and 2 contain zigzag chains of metal centers bridged by a single Hpdc2- ligand, whereas structure 6 consists of linear chains of metal centers bridged by two H2pdc- ligands. A dimer molecule [Sr(H3pdc)(H2pdc)2 (H2O)3]2·2 (H3pdc)·4H2O (4) was obtained from a similar hydrothermal reaction using Sr(ClO4)2·6H2O instead of MCl2. This compound contains [2+2] metallomacrocycles: At higher pH levels (pH = 4-6), the three-dimensional polymers [M(Hpdc)(H2O)] (Ca 3, Sr 5, Ba 7) were isolated by reactions of MCl2 (M = Ca, Sr, Ba) with H3pdc in water/Et3N or in M(OH)2 (M = Ca, Sr, Ba) with H3pdc in water under hydro(solvo)thermal conditions (150 °C, 3 days). Calcium and strontium are seven- and nine-coordinated in 3 and 5, respectively; barium is nine- and ten-coordinated in 7. It was observed that the increase in pH resulted in a higher connectivity level of ligands, which in turn leads to a higher dimensionality of the crystal structures. The correlation between the structures and pH values will be discussed. Crystal data: for 1, monoclinic, space group P21/n (No. 14), with a = 8.382(2), b = 12.621(3), c = 11.767(2) Å, β = 98.91(3)°, Z = 4; for 2, 3, and 5, monoclinic, space group P21/c (No. 14), Z = 4, a = 7.711(2), b = 15.574(3), c = 9.341(2) Å, β = 96.73(3)°, Z = 4 (2), a = 6.616(1), b = 12.654(3), c = 8.782(2) Å, β = 103.65(3)°, Z = 4 (3), a = 9.213(2), b = 12.088(3), c = 6.196(2) Å, β = 98.96(3)° (5); for 4 and 7, triclinic, space group P (No. 2), with a = 11.263(2), b = 11.460(3), c = 12.904(2) Å, α = 71.54(3), β 98.96(3), γ = 89.03(3)°, Z = 1 (4), a = 7.107(1), b = 9.780(2), c = 11.431(2) Å, α = 74.69(3), β = 73.39(3), γ = 85.29(3)°, Z = 2 (7); for 6, monoclinic, space group C2/c (No. 15), with a = 20.493(4), b = 6.708(1), c = 15.939(3) Å, β = 123.56(3)°, Z = 4.

AB - Hydrothermal reactions of simple alkaline salts or their hydroxides with 3,5-pyrazoledicarboxylic acid (H3pdc) yielded seven new compounds. At a lower pH level three one-dimeinsional structures [Ca(Hpdc)(H2O)4]·2H2O (1), [Ca(Hpdc)(H2O)4]·H2O (2), and [Ba(H2pdc)2(H2O)4] ·2H2O (6) were obtained by evaporation of the solutions resulting from hydro(solvo)thermal reactions of MCl2 (M = Ca, Ba) with H3pdc in water (1, 6) or in water/Et3N (2) at 150 °C for 3 days. Crystal structures of 1 and 2 contain zigzag chains of metal centers bridged by a single Hpdc2- ligand, whereas structure 6 consists of linear chains of metal centers bridged by two H2pdc- ligands. A dimer molecule [Sr(H3pdc)(H2pdc)2 (H2O)3]2·2 (H3pdc)·4H2O (4) was obtained from a similar hydrothermal reaction using Sr(ClO4)2·6H2O instead of MCl2. This compound contains [2+2] metallomacrocycles: At higher pH levels (pH = 4-6), the three-dimensional polymers [M(Hpdc)(H2O)] (Ca 3, Sr 5, Ba 7) were isolated by reactions of MCl2 (M = Ca, Sr, Ba) with H3pdc in water/Et3N or in M(OH)2 (M = Ca, Sr, Ba) with H3pdc in water under hydro(solvo)thermal conditions (150 °C, 3 days). Calcium and strontium are seven- and nine-coordinated in 3 and 5, respectively; barium is nine- and ten-coordinated in 7. It was observed that the increase in pH resulted in a higher connectivity level of ligands, which in turn leads to a higher dimensionality of the crystal structures. The correlation between the structures and pH values will be discussed. Crystal data: for 1, monoclinic, space group P21/n (No. 14), with a = 8.382(2), b = 12.621(3), c = 11.767(2) Å, β = 98.91(3)°, Z = 4; for 2, 3, and 5, monoclinic, space group P21/c (No. 14), Z = 4, a = 7.711(2), b = 15.574(3), c = 9.341(2) Å, β = 96.73(3)°, Z = 4 (2), a = 6.616(1), b = 12.654(3), c = 8.782(2) Å, β = 103.65(3)°, Z = 4 (3), a = 9.213(2), b = 12.088(3), c = 6.196(2) Å, β = 98.96(3)° (5); for 4 and 7, triclinic, space group P (No. 2), with a = 11.263(2), b = 11.460(3), c = 12.904(2) Å, α = 71.54(3), β 98.96(3), γ = 89.03(3)°, Z = 1 (4), a = 7.107(1), b = 9.780(2), c = 11.431(2) Å, α = 74.69(3), β = 73.39(3), γ = 85.29(3)°, Z = 2 (7); for 6, monoclinic, space group C2/c (No. 15), with a = 20.493(4), b = 6.708(1), c = 15.939(3) Å, β = 123.56(3)°, Z = 4.

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