Synthesis and characterization of uranyl compounds with iminodiacetate and oxydiacetate displaying variable denticity

J. Jiang, M. J. Sarsfield, J. C. Renshaw, F. R. Livens, D. Collison, J. M. Charnock, M. Helliwell, H. Eccles

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Abstract

Eight uranyl compounds containing the dicarboxylate ligands iminodiacetate (IDA) or oxydiacetate (ODA) have been characterized in the solid state. The published polymeric structures for [UO2(C4H6NO4)2] and [UO2(C4H4O5)]n have been confirmed, while Ba[UO2(C4H5NO4)2] ·3H2O, [(CH3)2NH(CH2)2 NH(CH3)2][UO2(C4H4 O5)2] [orthorhombic space group Pnma, a = 10.996(5) Å, b = 21.42(1) Å, c = 8.700(3) Å, Z = 4], and [C2H5NH2(CH2)2NH 2C2H5][UO2 (C4H4O5)2] [monoclinic space group P21/n, a = 6.857(3) Å, b = 9.209(5) Å, c = 16.410(7) Å, β = 91.69(3), Z = 2] contain monomeric anions. The distance from the uranium atom to the central heteroatom (O or N) in the ligand varies. Crystallographic study shows that U-heteroatom (O/N) distances fall into two groups, one 2.6-2.7 Å in length and one 3.1-3.2 Å, the latter implying no bonding interaction. By contrast, EXAFS analysis of bulk samples suggests that either a long U-heteroatom (O/N) distance (2.9 Å) or a range of distances may be present. Three possible structural types, two symmetric and one asymmetric, are identified on the basis of these results and on solid-state 13C NMR spectroscopy. The two ligands in the complex can be 1,4,7-tridentate, giving five-membered rings, or 1,7-bidentate, to form an eight-membered ring. (C4H12N2) [(UO2)2(C4H5 NO4)2(OH)2]·8H2O, [monoclinic space group P21/a, a = 7.955(9) Å, b = 24.050(8) Å, c = 8.223(6) Å, β = 112.24(6), Z = 2], (C2H10N2) [(UO2)2(C4H5 NO4)2(OH)2]·4H2O, and (C6H13N4)2 [(UO2)2 (C4H4O5)2(OH)2] ·2H2O [monoclinic space group C2/m, a = 19.024-(9) Å, b = 7.462(4) Å, c = 2.467(6) Å, β = 107.75(4), Z = 4] have a dimeric structure with two capping tridentate ligands and two μ2-hydroxo bridges, giving edge-sharing pentagonal bipyramids.

LanguageEnglish
Pages2799-2806
Number of pages8
JournalInorganic Chemistry
Volume41
Issue number10
Early online date26 Apr 2002
DOIs
Publication statusPublished - 2002

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Ligands
synthesis
ligands
Uranium
solid state
Nuclear magnetic resonance spectroscopy
rings
Anions
uranium
Atoms
anions
nuclear magnetic resonance
spectroscopy
atoms
interactions

Keywords

  • synthesis
  • characterization
  • uranyl compounds
  • iminodiacetate
  • oxydiacetate displaying variable denticity

Cite this

Jiang, J. ; Sarsfield, M. J. ; Renshaw, J. C. ; Livens, F. R. ; Collison, D. ; Charnock, J. M. ; Helliwell, M. ; Eccles, H. / Synthesis and characterization of uranyl compounds with iminodiacetate and oxydiacetate displaying variable denticity. In: Inorganic Chemistry. 2002 ; Vol. 41, No. 10. pp. 2799-2806.
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title = "Synthesis and characterization of uranyl compounds with iminodiacetate and oxydiacetate displaying variable denticity",
abstract = "Eight uranyl compounds containing the dicarboxylate ligands iminodiacetate (IDA) or oxydiacetate (ODA) have been characterized in the solid state. The published polymeric structures for [UO2(C4H6NO4)2] and [UO2(C4H4O5)]n have been confirmed, while Ba[UO2(C4H5NO4)2] ·3H2O, [(CH3)2NH(CH2)2 NH(CH3)2][UO2(C4H4 O5)2] [orthorhombic space group Pnma, a = 10.996(5) {\AA}, b = 21.42(1) {\AA}, c = 8.700(3) {\AA}, Z = 4], and [C2H5NH2(CH2)2NH 2C2H5][UO2 (C4H4O5)2] [monoclinic space group P21/n, a = 6.857(3) {\AA}, b = 9.209(5) {\AA}, c = 16.410(7) {\AA}, β = 91.69(3), Z = 2] contain monomeric anions. The distance from the uranium atom to the central heteroatom (O or N) in the ligand varies. Crystallographic study shows that U-heteroatom (O/N) distances fall into two groups, one 2.6-2.7 {\AA} in length and one 3.1-3.2 {\AA}, the latter implying no bonding interaction. By contrast, EXAFS analysis of bulk samples suggests that either a long U-heteroatom (O/N) distance (2.9 {\AA}) or a range of distances may be present. Three possible structural types, two symmetric and one asymmetric, are identified on the basis of these results and on solid-state 13C NMR spectroscopy. The two ligands in the complex can be 1,4,7-tridentate, giving five-membered rings, or 1,7-bidentate, to form an eight-membered ring. (C4H12N2) [(UO2)2(C4H5 NO4)2(OH)2]·8H2O, [monoclinic space group P21/a, a = 7.955(9) {\AA}, b = 24.050(8) {\AA}, c = 8.223(6) {\AA}, β = 112.24(6), Z = 2], (C2H10N2) [(UO2)2(C4H5 NO4)2(OH)2]·4H2O, and (C6H13N4)2 [(UO2)2 (C4H4O5)2(OH)2] ·2H2O [monoclinic space group C2/m, a = 19.024-(9) {\AA}, b = 7.462(4) {\AA}, c = 2.467(6) {\AA}, β = 107.75(4), Z = 4] have a dimeric structure with two capping tridentate ligands and two μ2-hydroxo bridges, giving edge-sharing pentagonal bipyramids.",
keywords = "synthesis, characterization, uranyl compounds, iminodiacetate, oxydiacetate displaying variable denticity",
author = "J. Jiang and Sarsfield, {M. J.} and Renshaw, {J. C.} and Livens, {F. R.} and D. Collison and Charnock, {J. M.} and M. Helliwell and H. Eccles",
year = "2002",
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journal = "Inorganic Chemistry",
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Jiang, J, Sarsfield, MJ, Renshaw, JC, Livens, FR, Collison, D, Charnock, JM, Helliwell, M & Eccles, H 2002, 'Synthesis and characterization of uranyl compounds with iminodiacetate and oxydiacetate displaying variable denticity' Inorganic Chemistry, vol. 41, no. 10, pp. 2799-2806. https://doi.org/10.1021/ic020121v

Synthesis and characterization of uranyl compounds with iminodiacetate and oxydiacetate displaying variable denticity. / Jiang, J.; Sarsfield, M. J.; Renshaw, J. C.; Livens, F. R.; Collison, D.; Charnock, J. M.; Helliwell, M.; Eccles, H.

In: Inorganic Chemistry, Vol. 41, No. 10, 2002, p. 2799-2806.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Synthesis and characterization of uranyl compounds with iminodiacetate and oxydiacetate displaying variable denticity

AU - Jiang, J.

AU - Sarsfield, M. J.

AU - Renshaw, J. C.

AU - Livens, F. R.

AU - Collison, D.

AU - Charnock, J. M.

AU - Helliwell, M.

AU - Eccles, H.

PY - 2002

Y1 - 2002

N2 - Eight uranyl compounds containing the dicarboxylate ligands iminodiacetate (IDA) or oxydiacetate (ODA) have been characterized in the solid state. The published polymeric structures for [UO2(C4H6NO4)2] and [UO2(C4H4O5)]n have been confirmed, while Ba[UO2(C4H5NO4)2] ·3H2O, [(CH3)2NH(CH2)2 NH(CH3)2][UO2(C4H4 O5)2] [orthorhombic space group Pnma, a = 10.996(5) Å, b = 21.42(1) Å, c = 8.700(3) Å, Z = 4], and [C2H5NH2(CH2)2NH 2C2H5][UO2 (C4H4O5)2] [monoclinic space group P21/n, a = 6.857(3) Å, b = 9.209(5) Å, c = 16.410(7) Å, β = 91.69(3), Z = 2] contain monomeric anions. The distance from the uranium atom to the central heteroatom (O or N) in the ligand varies. Crystallographic study shows that U-heteroatom (O/N) distances fall into two groups, one 2.6-2.7 Å in length and one 3.1-3.2 Å, the latter implying no bonding interaction. By contrast, EXAFS analysis of bulk samples suggests that either a long U-heteroatom (O/N) distance (2.9 Å) or a range of distances may be present. Three possible structural types, two symmetric and one asymmetric, are identified on the basis of these results and on solid-state 13C NMR spectroscopy. The two ligands in the complex can be 1,4,7-tridentate, giving five-membered rings, or 1,7-bidentate, to form an eight-membered ring. (C4H12N2) [(UO2)2(C4H5 NO4)2(OH)2]·8H2O, [monoclinic space group P21/a, a = 7.955(9) Å, b = 24.050(8) Å, c = 8.223(6) Å, β = 112.24(6), Z = 2], (C2H10N2) [(UO2)2(C4H5 NO4)2(OH)2]·4H2O, and (C6H13N4)2 [(UO2)2 (C4H4O5)2(OH)2] ·2H2O [monoclinic space group C2/m, a = 19.024-(9) Å, b = 7.462(4) Å, c = 2.467(6) Å, β = 107.75(4), Z = 4] have a dimeric structure with two capping tridentate ligands and two μ2-hydroxo bridges, giving edge-sharing pentagonal bipyramids.

AB - Eight uranyl compounds containing the dicarboxylate ligands iminodiacetate (IDA) or oxydiacetate (ODA) have been characterized in the solid state. The published polymeric structures for [UO2(C4H6NO4)2] and [UO2(C4H4O5)]n have been confirmed, while Ba[UO2(C4H5NO4)2] ·3H2O, [(CH3)2NH(CH2)2 NH(CH3)2][UO2(C4H4 O5)2] [orthorhombic space group Pnma, a = 10.996(5) Å, b = 21.42(1) Å, c = 8.700(3) Å, Z = 4], and [C2H5NH2(CH2)2NH 2C2H5][UO2 (C4H4O5)2] [monoclinic space group P21/n, a = 6.857(3) Å, b = 9.209(5) Å, c = 16.410(7) Å, β = 91.69(3), Z = 2] contain monomeric anions. The distance from the uranium atom to the central heteroatom (O or N) in the ligand varies. Crystallographic study shows that U-heteroatom (O/N) distances fall into two groups, one 2.6-2.7 Å in length and one 3.1-3.2 Å, the latter implying no bonding interaction. By contrast, EXAFS analysis of bulk samples suggests that either a long U-heteroatom (O/N) distance (2.9 Å) or a range of distances may be present. Three possible structural types, two symmetric and one asymmetric, are identified on the basis of these results and on solid-state 13C NMR spectroscopy. The two ligands in the complex can be 1,4,7-tridentate, giving five-membered rings, or 1,7-bidentate, to form an eight-membered ring. (C4H12N2) [(UO2)2(C4H5 NO4)2(OH)2]·8H2O, [monoclinic space group P21/a, a = 7.955(9) Å, b = 24.050(8) Å, c = 8.223(6) Å, β = 112.24(6), Z = 2], (C2H10N2) [(UO2)2(C4H5 NO4)2(OH)2]·4H2O, and (C6H13N4)2 [(UO2)2 (C4H4O5)2(OH)2] ·2H2O [monoclinic space group C2/m, a = 19.024-(9) Å, b = 7.462(4) Å, c = 2.467(6) Å, β = 107.75(4), Z = 4] have a dimeric structure with two capping tridentate ligands and two μ2-hydroxo bridges, giving edge-sharing pentagonal bipyramids.

KW - synthesis

KW - characterization

KW - uranyl compounds

KW - iminodiacetate

KW - oxydiacetate displaying variable denticity

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U2 - 10.1021/ic020121v

DO - 10.1021/ic020121v

M3 - Article

VL - 41

SP - 2799

EP - 2806

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T2 - Inorganic Chemistry

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SN - 0020-1669

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