Hydrothermal Synthesis and Characterization of Hexavanadium Polyoxo Alkoxide Anion Clusters: Crystal Structures of the Vanadium(IV) Species Ba[V6O7(OH)3{(OCH2)3CCH3}3]·3H2O and Na2[V6O7{(OCH2)3CCH2CH3}4], of the Mixed-Valence Complex (Me3NH)[VIV5VVO7(OH)3{(OCH2)3CCH3}3], and of the Fluoro Derivative Na[V6O6F(OH)3{(OCH2)3CCH3}3]·3H2O

M. Ishaque Khan; Qin Chen; Hakon Höpe; Sean Parkin; Charles J. O'Connor; Jon Zubieta

doi:10.1021/ic00065a022

Hydrothermal Synthesis and Characterization of Hexavanadium Polyoxo Alkoxide Anion Clusters: Crystal Structures of the Vanadium(IV) Species Ba[V₆O₇(OH)₃{(OCH₂)₃CCH₃}₃]·3H₂O and Na₂[V₆O₇{(OCH₂)₃CCH₂CH₃}₄], of the Mixed-Valence Complex (Me₃NH)[V^IV₅V^VO₇(OH)₃{(OCH₂)₃CCH₃}₃], and of the Fluoro Derivative Na[V₆O₆F(OH)₃{(OCH₂)₃CCH₃}₃]·3H₂O

M. Ishaque Khan, Qin Chen, Hakon Höpe, Sean Parkin, Charles J. O'Connor, Jon Zubieta

Department of Chemistry

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82 Scopus citations

Abstract

The hydrothermal reactions of vanadium oxide precursors with trialkoxy ligands of the class (HOCH₂)₃CR (R = CH₃, CH₂CH₃) yield polyalkoxyoxovanadium clusters with a hexametalate core, Ba[V₆O₇(OH)₃{(OCH₂)₃CCH₃}₃]·3H₂O (1), Na₂[V₆O₇{(OCH₂)₃CCH₂CH₃}₄] (2), (Me₃NH)[V₆O₇(OH)₃{(OCH₂)₃CCH₃}₃] (3), and Na[V₆O₆F(OH)₃{(OCH₂)3CCH₃}₃]·3H₂O (4). Cluster 1 is a fully-reduced V(IV) species in which nine doubly bridging oxo groups of the parent {V₆O₁₉} core have been substituted by alkoxy oxygen donors of the three trialkoxy ligands. The structure of 3 is grossly similar to that of 1, with differences in metrical parameters reflecting the presence of one oxidized V(V) site in the metal core of 3. The fully reduced cluster 2 exhibits complete substitution of the doubly-bridging oxo groups of the parent core by 12 ligand alkoxy donors. The tendency of polyvanadium oxide clusters to encapsulate a variety of guest molecules or ions is demonstrated by the structure of 4, in which the central μ₆-oxo group of the parent core has been substituted by a μ₃-fluoride, resulting in a considerably distorted {V₆O₆-(μ₃-F)(μ₂-OH)₃(μ₂-OR)₉} core. Crystal data for 1: hexagonal space group P6₃mc, a = 13.707(1) Å, c = 9.647(2) Å, V = 1569.7(2) Å³, Z = 2, D_calc = 2.140 g cm⁻³; structure solution and refinement based on 399 reflections converged at R = 0.0576. Crystal data for 2: cubic space group Fd3, a = 19.202(4) Å, V= 7080(1) Å³, Z = 8, D_calc = 1.749 g cm⁻³; 293 reflections, R = 0.0509. Crystal data for 3: hexagonal space group P6₃mc, a = 12.792(3) Å, c = 10.692(2) Å, V= 1515.2(6) Å³, Z = 2, D_calc = 1.929 g cm⁻³; 651 reflections, R = 0.0410. Crystal data for 4: hexagonal space group P6₃mc, a = 12.977(1) Å, c = 10.160(1) Å, V= 1481.7(2) Å³, Z = 2, D_calc = 2.020 g cm⁻³; 379 reflections, R = 0.0371.

Original language	English (US)
Pages (from-to)	2929-2937
Number of pages	9
Journal	Inorganic Chemistry
Volume	32
Issue number	13
DOIs	https://doi.org/10.1021/ic00065a022
State	Published - 1993

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Physical and Theoretical Chemistry
Inorganic Chemistry

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Dive into the research topics of 'Hydrothermal Synthesis and Characterization of Hexavanadium Polyoxo Alkoxide Anion Clusters: Crystal Structures of the Vanadium(IV) Species Ba[V₆O₇(OH)₃{(OCH₂)₃CCH₃}₃]·3H₂O and Na₂[V₆O₇{(OCH₂)₃CCH₂CH₃}₄], of the Mixed-Valence Complex (Me₃NH)[V^IV₅V^VO₇(OH)₃{(OCH₂)₃CCH₃}₃], and of the Fluoro Derivative Na[V₆O₆F(OH)₃{(OCH₂)₃CCH₃}₃]·3H₂O'. Together they form a unique fingerprint.

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Khan, M. I., Chen, Q., Höpe, H., Parkin, S., O'Connor, C. J., & Zubieta, J. (1993). Hydrothermal Synthesis and Characterization of Hexavanadium Polyoxo Alkoxide Anion Clusters: Crystal Structures of the Vanadium(IV) Species Ba[V₆O₇(OH)₃{(OCH₂)₃CCH₃}₃]·3H₂O and Na₂[V₆O₇{(OCH₂)₃CCH₂CH₃}₄], of the Mixed-Valence Complex (Me₃NH)[V^IV₅V^VO₇(OH)₃{(OCH₂)₃CCH₃}₃], and of the Fluoro Derivative Na[V₆O₆F(OH)₃{(OCH₂)₃CCH₃}₃]·3H₂O. Inorganic Chemistry, 32(13), 2929-2937. https://doi.org/10.1021/ic00065a022

Hydrothermal Synthesis and Characterization of Hexavanadium Polyoxo Alkoxide Anion Clusters: Crystal Structures of the Vanadium(IV) Species Ba[V₆O₇(OH)₃{(OCH₂)₃CCH₃}₃]·3H₂O and Na₂[V₆O₇{(OCH₂)₃CCH₂CH₃}₄], of the Mixed-Valence Complex (Me₃NH)[V^IV₅V^VO₇(OH)₃{(OCH₂)₃CCH₃}₃], and of the Fluoro Derivative Na[V₆O₆F(OH)₃{(OCH₂)₃CCH₃}₃]·3H₂O. / Khan, M. Ishaque; Chen, Qin; Höpe, Hakon et al.
In: Inorganic Chemistry, Vol. 32, No. 13, 1993, p. 2929-2937.

Research output: Contribution to journal › Article › peer-review

Khan, MI, Chen, Q, Höpe, H, Parkin, S, O'Connor, CJ & Zubieta, J 1993, 'Hydrothermal Synthesis and Characterization of Hexavanadium Polyoxo Alkoxide Anion Clusters: Crystal Structures of the Vanadium(IV) Species Ba[V₆O₇(OH)₃{(OCH₂)₃CCH₃}₃]·3H₂O and Na₂[V₆O₇{(OCH₂)₃CCH₂CH₃}₄], of the Mixed-Valence Complex (Me₃NH)[V^IV₅V^VO₇(OH)₃{(OCH₂)₃CCH₃}₃], and of the Fluoro Derivative Na[V₆O₆F(OH)₃{(OCH₂)₃CCH₃}₃]·3H₂O', Inorganic Chemistry, vol. 32, no. 13, pp. 2929-2937. https://doi.org/10.1021/ic00065a022

Khan MI, Chen Q, Höpe H, Parkin S, O'Connor CJ, Zubieta J. Hydrothermal Synthesis and Characterization of Hexavanadium Polyoxo Alkoxide Anion Clusters: Crystal Structures of the Vanadium(IV) Species Ba[V₆O₇(OH)₃{(OCH₂)₃CCH₃}₃]·3H₂O and Na₂[V₆O₇{(OCH₂)₃CCH₂CH₃}₄], of the Mixed-Valence Complex (Me₃NH)[V^IV₅V^VO₇(OH)₃{(OCH₂)₃CCH₃}₃], and of the Fluoro Derivative Na[V₆O₆F(OH)₃{(OCH₂)₃CCH₃}₃]·3H₂O. Inorganic Chemistry. 1993;32(13):2929-2937. doi: 10.1021/ic00065a022

Khan, M. Ishaque ; Chen, Qin ; Höpe, Hakon et al. / Hydrothermal Synthesis and Characterization of Hexavanadium Polyoxo Alkoxide Anion Clusters : Crystal Structures of the Vanadium(IV) Species Ba[V₆O₇(OH)₃{(OCH₂)₃CCH₃}₃]·3H₂O and Na₂[V₆O₇{(OCH₂)₃CCH₂CH₃}₄], of the Mixed-Valence Complex (Me₃NH)[V^IV₅V^VO₇(OH)₃{(OCH₂)₃CCH₃}₃], and of the Fluoro Derivative Na[V₆O₆F(OH)₃{(OCH₂)₃CCH₃}₃]·3H₂O. In: Inorganic Chemistry. 1993 ; Vol. 32, No. 13. pp. 2929-2937.

@article{59da67efd06d488f90e756a09f2ee104,

title = "Hydrothermal Synthesis and Characterization of Hexavanadium Polyoxo Alkoxide Anion Clusters: Crystal Structures of the Vanadium(IV) Species Ba[V6O7(OH)3{(OCH2)3CCH3}3]·3H2O and Na2[V6O7{(OCH2)3CCH2CH3}4], of the Mixed-Valence Complex (Me3NH)[VIV5VVO7(OH)3{(OCH2)3CCH3}3], and of the Fluoro Derivative Na[V6O6F(OH)3{(OCH2)3CCH3}3]·3H2O",

abstract = "The hydrothermal reactions of vanadium oxide precursors with trialkoxy ligands of the class (HOCH2)3CR (R = CH3, CH2CH3) yield polyalkoxyoxovanadium clusters with a hexametalate core, Ba[V6O7(OH)3{(OCH2)3CCH3}3]·3H2O (1), Na2[V6O7{(OCH2)3CCH2CH3}4] (2), (Me3NH)[V6O7(OH)3{(OCH2)3CCH3}3] (3), and Na[V6O6F(OH)3{(OCH2)3CCH3}3]·3H2O (4). Cluster 1 is a fully-reduced V(IV) species in which nine doubly bridging oxo groups of the parent {V6O19} core have been substituted by alkoxy oxygen donors of the three trialkoxy ligands. The structure of 3 is grossly similar to that of 1, with differences in metrical parameters reflecting the presence of one oxidized V(V) site in the metal core of 3. The fully reduced cluster 2 exhibits complete substitution of the doubly-bridging oxo groups of the parent core by 12 ligand alkoxy donors. The tendency of polyvanadium oxide clusters to encapsulate a variety of guest molecules or ions is demonstrated by the structure of 4, in which the central μ6-oxo group of the parent core has been substituted by a μ3-fluoride, resulting in a considerably distorted {V6O6-(μ3-F)(μ2-OH)3(μ2-OR)9} core. Crystal data for 1: hexagonal space group P63mc, a = 13.707(1) {\AA}, c = 9.647(2) {\AA}, V = 1569.7(2) {\AA}3, Z = 2, Dcalc = 2.140 g cm−3; structure solution and refinement based on 399 reflections converged at R = 0.0576. Crystal data for 2: cubic space group Fd3, a = 19.202(4) {\AA}, V= 7080(1) {\AA}3, Z = 8, Dcalc = 1.749 g cm−3; 293 reflections, R = 0.0509. Crystal data for 3: hexagonal space group P63mc, a = 12.792(3) {\AA}, c = 10.692(2) {\AA}, V= 1515.2(6) {\AA}3, Z = 2, Dcalc = 1.929 g cm−3; 651 reflections, R = 0.0410. Crystal data for 4: hexagonal space group P63mc, a = 12.977(1) {\AA}, c = 10.160(1) {\AA}, V= 1481.7(2) {\AA}3, Z = 2, Dcalc = 2.020 g cm−3; 379 reflections, R = 0.0371.",

author = "Khan, {M. Ishaque} and Qin Chen and Hakon H{\"o}pe and Sean Parkin and O'Connor, {Charles J.} and Jon Zubieta",

year = "1993",

doi = "10.1021/ic00065a022",

language = "English (US)",

volume = "32",

pages = "2929--2937",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

number = "13",

}

TY - JOUR

T1 - Hydrothermal Synthesis and Characterization of Hexavanadium Polyoxo Alkoxide Anion Clusters

T2 - Crystal Structures of the Vanadium(IV) Species Ba[V6O7(OH)3{(OCH2)3CCH3}3]·3H2O and Na2[V6O7{(OCH2)3CCH2CH3}4], of the Mixed-Valence Complex (Me3NH)[VIV5VVO7(OH)3{(OCH2)3CCH3}3], and of the Fluoro Derivative Na[V6O6F(OH)3{(OCH2)3CCH3}3]·3H2O

AU - Khan, M. Ishaque

AU - Chen, Qin

AU - Höpe, Hakon

AU - Parkin, Sean

AU - O'Connor, Charles J.

AU - Zubieta, Jon

PY - 1993

Y1 - 1993

N2 - The hydrothermal reactions of vanadium oxide precursors with trialkoxy ligands of the class (HOCH2)3CR (R = CH3, CH2CH3) yield polyalkoxyoxovanadium clusters with a hexametalate core, Ba[V6O7(OH)3{(OCH2)3CCH3}3]·3H2O (1), Na2[V6O7{(OCH2)3CCH2CH3}4] (2), (Me3NH)[V6O7(OH)3{(OCH2)3CCH3}3] (3), and Na[V6O6F(OH)3{(OCH2)3CCH3}3]·3H2O (4). Cluster 1 is a fully-reduced V(IV) species in which nine doubly bridging oxo groups of the parent {V6O19} core have been substituted by alkoxy oxygen donors of the three trialkoxy ligands. The structure of 3 is grossly similar to that of 1, with differences in metrical parameters reflecting the presence of one oxidized V(V) site in the metal core of 3. The fully reduced cluster 2 exhibits complete substitution of the doubly-bridging oxo groups of the parent core by 12 ligand alkoxy donors. The tendency of polyvanadium oxide clusters to encapsulate a variety of guest molecules or ions is demonstrated by the structure of 4, in which the central μ6-oxo group of the parent core has been substituted by a μ3-fluoride, resulting in a considerably distorted {V6O6-(μ3-F)(μ2-OH)3(μ2-OR)9} core. Crystal data for 1: hexagonal space group P63mc, a = 13.707(1) Å, c = 9.647(2) Å, V = 1569.7(2) Å3, Z = 2, Dcalc = 2.140 g cm−3; structure solution and refinement based on 399 reflections converged at R = 0.0576. Crystal data for 2: cubic space group Fd3, a = 19.202(4) Å, V= 7080(1) Å3, Z = 8, Dcalc = 1.749 g cm−3; 293 reflections, R = 0.0509. Crystal data for 3: hexagonal space group P63mc, a = 12.792(3) Å, c = 10.692(2) Å, V= 1515.2(6) Å3, Z = 2, Dcalc = 1.929 g cm−3; 651 reflections, R = 0.0410. Crystal data for 4: hexagonal space group P63mc, a = 12.977(1) Å, c = 10.160(1) Å, V= 1481.7(2) Å3, Z = 2, Dcalc = 2.020 g cm−3; 379 reflections, R = 0.0371.

AB - The hydrothermal reactions of vanadium oxide precursors with trialkoxy ligands of the class (HOCH2)3CR (R = CH3, CH2CH3) yield polyalkoxyoxovanadium clusters with a hexametalate core, Ba[V6O7(OH)3{(OCH2)3CCH3}3]·3H2O (1), Na2[V6O7{(OCH2)3CCH2CH3}4] (2), (Me3NH)[V6O7(OH)3{(OCH2)3CCH3}3] (3), and Na[V6O6F(OH)3{(OCH2)3CCH3}3]·3H2O (4). Cluster 1 is a fully-reduced V(IV) species in which nine doubly bridging oxo groups of the parent {V6O19} core have been substituted by alkoxy oxygen donors of the three trialkoxy ligands. The structure of 3 is grossly similar to that of 1, with differences in metrical parameters reflecting the presence of one oxidized V(V) site in the metal core of 3. The fully reduced cluster 2 exhibits complete substitution of the doubly-bridging oxo groups of the parent core by 12 ligand alkoxy donors. The tendency of polyvanadium oxide clusters to encapsulate a variety of guest molecules or ions is demonstrated by the structure of 4, in which the central μ6-oxo group of the parent core has been substituted by a μ3-fluoride, resulting in a considerably distorted {V6O6-(μ3-F)(μ2-OH)3(μ2-OR)9} core. Crystal data for 1: hexagonal space group P63mc, a = 13.707(1) Å, c = 9.647(2) Å, V = 1569.7(2) Å3, Z = 2, Dcalc = 2.140 g cm−3; structure solution and refinement based on 399 reflections converged at R = 0.0576. Crystal data for 2: cubic space group Fd3, a = 19.202(4) Å, V= 7080(1) Å3, Z = 8, Dcalc = 1.749 g cm−3; 293 reflections, R = 0.0509. Crystal data for 3: hexagonal space group P63mc, a = 12.792(3) Å, c = 10.692(2) Å, V= 1515.2(6) Å3, Z = 2, Dcalc = 1.929 g cm−3; 651 reflections, R = 0.0410. Crystal data for 4: hexagonal space group P63mc, a = 12.977(1) Å, c = 10.160(1) Å, V= 1481.7(2) Å3, Z = 2, Dcalc = 2.020 g cm−3; 379 reflections, R = 0.0371.

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DO - 10.1021/ic00065a022

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JO - Inorganic Chemistry

JF - Inorganic Chemistry

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