Synthesis, pH-dependent structural characterization, and solution behavior of aqueous aluminum and gallium citrate complexes

M. Matzapetakis, M. Kourgiantakis, M. Dakanali, C. P. Raptopoulou, A. Terzis, A. Lakatos, T. Kiss, I. Bányai, L. Iordanidis, T. Mavromoustakos, A. Salifoglou

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Abstract

Reactions of Al(III) and Ga(III) with citric acid in aqueous solutions, yielded the complexes (NH4)5{M(C6H4 O7)2}·2H2O (M(III) = Al (1), Ga (2)) at alkaline pH, and the complexes (Cat)4{M(C6H5O7) (C6H4O7)}·nH2O (M(III) = Al (3), Ga (4), Cat. = NH4+, n = 3; M(III) = Al (5), Ga (6), Cat. = K+, n = 4) at acidic pH. All compounds were characterized by spectroscopic (FT-IR, 1H, 13C, and 27Al NMR, 13C-MAS NMR) and X-ray techniques. Complex 1 crystallizes in space group P1̄, with a = 9.638(5) Å, b = 9.715(5) Å, c = 7.237(4) Å, α = 90.96(1)°, β = 105.72(1)°, γ = 119.74(1)°, V = 557.1(3) Å3, and Z = 1. Complex 2 crystallizes in space group P1̄, with a = 9.659(6) Å, b = 9.762(7) Å, c = 7.258(5) Å, α = 90.95(2)°, β = 105.86(2)°, γ = 119.28(1)°, V = 564.9(7) Å3, and Z = 1. Complex 3 crystallizes in space group I2/a, with a = 19.347(3) Å, b = 9.857(1) Å, c = 23.412(4) Å, β = 100.549(5)°, V = 4389(1) Å3, and Z = 8. Complex 4 crystallizes in space group I2/a, with a = 19.275(1) Å, b = 9.9697(6) Å, c = 23.476(1) Å, β = 100.694(2)°, V = 4432.8(5 ) Å3, and Z = 8. Complex 5 crystallizes in space group P1̄, with a = 7.316(1) Å, b = 9.454(2) Å, c = 9.569(2) Å, α = 64.218(4)°, β = 69.872(3)°, γ = 69.985(4)°, V = 544.9(2) Å3, and Z = 1. Complex 6 crystallizes in space group P1̄, with a = 7.3242(2) Å, b = 9.4363(5) Å, c = 9.6435(5) Å, α = 63.751(2)°, β = 70.091(2)°, γ = 69.941(2)° V = 547.22(4) Å3, and Z = 1. The crystal structures of 1-6 reveal mononuclear octahedral complexes of Al(III) (or Ga(III)) bound to two citrates. Solution NMR, on both 4- and 5- species, reveals rapid intramolecular exchange of the bound and unbound terminal carboxylates. Upon dissolution in water, the complexes, through a complicated reaction cascade, transform to oligonuclear 1:1 species that, in agreement with previous studies, represent the thermodynamically stable state in solution. The data provide, for the first time, structural details of low MW, mononuclear complexes of Al(III) (or Ga(III)) with citrate that are dictated, among other factors, by pH. The properties of 1-6 may provide clues relevant to their biological association with humans.

Original languageEnglish
Pages (from-to)1734-1744
Number of pages11
JournalInorganic Chemistry
Volume40
Issue number8
DOIs
Publication statusPublished - Apr 9 2001

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citrates
gallium
Nuclear magnetic resonance
aluminum
Citric Acid
Citrates
synthesis
nuclear magnetic resonance
Dissolution
Crystal structure
X rays
Water
citric acid
cats
carboxylates
aluminum citrate
gallium citrate
cascades
dissolving
aqueous solutions

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Matzapetakis, M., Kourgiantakis, M., Dakanali, M., Raptopoulou, C. P., Terzis, A., Lakatos, A., ... Salifoglou, A. (2001). Synthesis, pH-dependent structural characterization, and solution behavior of aqueous aluminum and gallium citrate complexes. Inorganic Chemistry, 40(8), 1734-1744. https://doi.org/10.1021/ic000461l

Synthesis, pH-dependent structural characterization, and solution behavior of aqueous aluminum and gallium citrate complexes. / Matzapetakis, M.; Kourgiantakis, M.; Dakanali, M.; Raptopoulou, C. P.; Terzis, A.; Lakatos, A.; Kiss, T.; Bányai, I.; Iordanidis, L.; Mavromoustakos, T.; Salifoglou, A.

In: Inorganic Chemistry, Vol. 40, No. 8, 09.04.2001, p. 1734-1744.

Research output: Contribution to journalArticle

Matzapetakis, M, Kourgiantakis, M, Dakanali, M, Raptopoulou, CP, Terzis, A, Lakatos, A, Kiss, T, Bányai, I, Iordanidis, L, Mavromoustakos, T & Salifoglou, A 2001, 'Synthesis, pH-dependent structural characterization, and solution behavior of aqueous aluminum and gallium citrate complexes', Inorganic Chemistry, vol. 40, no. 8, pp. 1734-1744. https://doi.org/10.1021/ic000461l
Matzapetakis, M. ; Kourgiantakis, M. ; Dakanali, M. ; Raptopoulou, C. P. ; Terzis, A. ; Lakatos, A. ; Kiss, T. ; Bányai, I. ; Iordanidis, L. ; Mavromoustakos, T. ; Salifoglou, A. / Synthesis, pH-dependent structural characterization, and solution behavior of aqueous aluminum and gallium citrate complexes. In: Inorganic Chemistry. 2001 ; Vol. 40, No. 8. pp. 1734-1744.
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title = "Synthesis, pH-dependent structural characterization, and solution behavior of aqueous aluminum and gallium citrate complexes",
abstract = "Reactions of Al(III) and Ga(III) with citric acid in aqueous solutions, yielded the complexes (NH4)5{M(C6H4 O7)2}·2H2O (M(III) = Al (1), Ga (2)) at alkaline pH, and the complexes (Cat)4{M(C6H5O7) (C6H4O7)}·nH2O (M(III) = Al (3), Ga (4), Cat. = NH4+, n = 3; M(III) = Al (5), Ga (6), Cat. = K+, n = 4) at acidic pH. All compounds were characterized by spectroscopic (FT-IR, 1H, 13C, and 27Al NMR, 13C-MAS NMR) and X-ray techniques. Complex 1 crystallizes in space group P1̄, with a = 9.638(5) {\AA}, b = 9.715(5) {\AA}, c = 7.237(4) {\AA}, α = 90.96(1)°, β = 105.72(1)°, γ = 119.74(1)°, V = 557.1(3) {\AA}3, and Z = 1. Complex 2 crystallizes in space group P1̄, with a = 9.659(6) {\AA}, b = 9.762(7) {\AA}, c = 7.258(5) {\AA}, α = 90.95(2)°, β = 105.86(2)°, γ = 119.28(1)°, V = 564.9(7) {\AA}3, and Z = 1. Complex 3 crystallizes in space group I2/a, with a = 19.347(3) {\AA}, b = 9.857(1) {\AA}, c = 23.412(4) {\AA}, β = 100.549(5)°, V = 4389(1) {\AA}3, and Z = 8. Complex 4 crystallizes in space group I2/a, with a = 19.275(1) {\AA}, b = 9.9697(6) {\AA}, c = 23.476(1) {\AA}, β = 100.694(2)°, V = 4432.8(5 ) {\AA}3, and Z = 8. Complex 5 crystallizes in space group P1̄, with a = 7.316(1) {\AA}, b = 9.454(2) {\AA}, c = 9.569(2) {\AA}, α = 64.218(4)°, β = 69.872(3)°, γ = 69.985(4)°, V = 544.9(2) {\AA}3, and Z = 1. Complex 6 crystallizes in space group P1̄, with a = 7.3242(2) {\AA}, b = 9.4363(5) {\AA}, c = 9.6435(5) {\AA}, α = 63.751(2)°, β = 70.091(2)°, γ = 69.941(2)° V = 547.22(4) {\AA}3, and Z = 1. The crystal structures of 1-6 reveal mononuclear octahedral complexes of Al(III) (or Ga(III)) bound to two citrates. Solution NMR, on both 4- and 5- species, reveals rapid intramolecular exchange of the bound and unbound terminal carboxylates. Upon dissolution in water, the complexes, through a complicated reaction cascade, transform to oligonuclear 1:1 species that, in agreement with previous studies, represent the thermodynamically stable state in solution. The data provide, for the first time, structural details of low MW, mononuclear complexes of Al(III) (or Ga(III)) with citrate that are dictated, among other factors, by pH. The properties of 1-6 may provide clues relevant to their biological association with humans.",
author = "M. Matzapetakis and M. Kourgiantakis and M. Dakanali and Raptopoulou, {C. P.} and A. Terzis and A. Lakatos and T. Kiss and I. B{\'a}nyai and L. Iordanidis and T. Mavromoustakos and A. Salifoglou",
year = "2001",
month = "4",
day = "9",
doi = "10.1021/ic000461l",
language = "English",
volume = "40",
pages = "1734--1744",
journal = "Inorganic Chemistry",
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TY - JOUR

T1 - Synthesis, pH-dependent structural characterization, and solution behavior of aqueous aluminum and gallium citrate complexes

AU - Matzapetakis, M.

AU - Kourgiantakis, M.

AU - Dakanali, M.

AU - Raptopoulou, C. P.

AU - Terzis, A.

AU - Lakatos, A.

AU - Kiss, T.

AU - Bányai, I.

AU - Iordanidis, L.

AU - Mavromoustakos, T.

AU - Salifoglou, A.

PY - 2001/4/9

Y1 - 2001/4/9

N2 - Reactions of Al(III) and Ga(III) with citric acid in aqueous solutions, yielded the complexes (NH4)5{M(C6H4 O7)2}·2H2O (M(III) = Al (1), Ga (2)) at alkaline pH, and the complexes (Cat)4{M(C6H5O7) (C6H4O7)}·nH2O (M(III) = Al (3), Ga (4), Cat. = NH4+, n = 3; M(III) = Al (5), Ga (6), Cat. = K+, n = 4) at acidic pH. All compounds were characterized by spectroscopic (FT-IR, 1H, 13C, and 27Al NMR, 13C-MAS NMR) and X-ray techniques. Complex 1 crystallizes in space group P1̄, with a = 9.638(5) Å, b = 9.715(5) Å, c = 7.237(4) Å, α = 90.96(1)°, β = 105.72(1)°, γ = 119.74(1)°, V = 557.1(3) Å3, and Z = 1. Complex 2 crystallizes in space group P1̄, with a = 9.659(6) Å, b = 9.762(7) Å, c = 7.258(5) Å, α = 90.95(2)°, β = 105.86(2)°, γ = 119.28(1)°, V = 564.9(7) Å3, and Z = 1. Complex 3 crystallizes in space group I2/a, with a = 19.347(3) Å, b = 9.857(1) Å, c = 23.412(4) Å, β = 100.549(5)°, V = 4389(1) Å3, and Z = 8. Complex 4 crystallizes in space group I2/a, with a = 19.275(1) Å, b = 9.9697(6) Å, c = 23.476(1) Å, β = 100.694(2)°, V = 4432.8(5 ) Å3, and Z = 8. Complex 5 crystallizes in space group P1̄, with a = 7.316(1) Å, b = 9.454(2) Å, c = 9.569(2) Å, α = 64.218(4)°, β = 69.872(3)°, γ = 69.985(4)°, V = 544.9(2) Å3, and Z = 1. Complex 6 crystallizes in space group P1̄, with a = 7.3242(2) Å, b = 9.4363(5) Å, c = 9.6435(5) Å, α = 63.751(2)°, β = 70.091(2)°, γ = 69.941(2)° V = 547.22(4) Å3, and Z = 1. The crystal structures of 1-6 reveal mononuclear octahedral complexes of Al(III) (or Ga(III)) bound to two citrates. Solution NMR, on both 4- and 5- species, reveals rapid intramolecular exchange of the bound and unbound terminal carboxylates. Upon dissolution in water, the complexes, through a complicated reaction cascade, transform to oligonuclear 1:1 species that, in agreement with previous studies, represent the thermodynamically stable state in solution. The data provide, for the first time, structural details of low MW, mononuclear complexes of Al(III) (or Ga(III)) with citrate that are dictated, among other factors, by pH. The properties of 1-6 may provide clues relevant to their biological association with humans.

AB - Reactions of Al(III) and Ga(III) with citric acid in aqueous solutions, yielded the complexes (NH4)5{M(C6H4 O7)2}·2H2O (M(III) = Al (1), Ga (2)) at alkaline pH, and the complexes (Cat)4{M(C6H5O7) (C6H4O7)}·nH2O (M(III) = Al (3), Ga (4), Cat. = NH4+, n = 3; M(III) = Al (5), Ga (6), Cat. = K+, n = 4) at acidic pH. All compounds were characterized by spectroscopic (FT-IR, 1H, 13C, and 27Al NMR, 13C-MAS NMR) and X-ray techniques. Complex 1 crystallizes in space group P1̄, with a = 9.638(5) Å, b = 9.715(5) Å, c = 7.237(4) Å, α = 90.96(1)°, β = 105.72(1)°, γ = 119.74(1)°, V = 557.1(3) Å3, and Z = 1. Complex 2 crystallizes in space group P1̄, with a = 9.659(6) Å, b = 9.762(7) Å, c = 7.258(5) Å, α = 90.95(2)°, β = 105.86(2)°, γ = 119.28(1)°, V = 564.9(7) Å3, and Z = 1. Complex 3 crystallizes in space group I2/a, with a = 19.347(3) Å, b = 9.857(1) Å, c = 23.412(4) Å, β = 100.549(5)°, V = 4389(1) Å3, and Z = 8. Complex 4 crystallizes in space group I2/a, with a = 19.275(1) Å, b = 9.9697(6) Å, c = 23.476(1) Å, β = 100.694(2)°, V = 4432.8(5 ) Å3, and Z = 8. Complex 5 crystallizes in space group P1̄, with a = 7.316(1) Å, b = 9.454(2) Å, c = 9.569(2) Å, α = 64.218(4)°, β = 69.872(3)°, γ = 69.985(4)°, V = 544.9(2) Å3, and Z = 1. Complex 6 crystallizes in space group P1̄, with a = 7.3242(2) Å, b = 9.4363(5) Å, c = 9.6435(5) Å, α = 63.751(2)°, β = 70.091(2)°, γ = 69.941(2)° V = 547.22(4) Å3, and Z = 1. The crystal structures of 1-6 reveal mononuclear octahedral complexes of Al(III) (or Ga(III)) bound to two citrates. Solution NMR, on both 4- and 5- species, reveals rapid intramolecular exchange of the bound and unbound terminal carboxylates. Upon dissolution in water, the complexes, through a complicated reaction cascade, transform to oligonuclear 1:1 species that, in agreement with previous studies, represent the thermodynamically stable state in solution. The data provide, for the first time, structural details of low MW, mononuclear complexes of Al(III) (or Ga(III)) with citrate that are dictated, among other factors, by pH. The properties of 1-6 may provide clues relevant to their biological association with humans.

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