Hydrothermal synthesis and crystal structures of two novel vanadium oxides containing interlamellar transition metal complexes

Patricia J. Ollivier, Jeffrey R.D. Deboard, Pamela J. Zapf, Jon Zubieta, Linda M. Meyer, Chwan Chin Wang, Thomas E. Mallouk, Robert C. Haushalter

Research output: Contribution to journalArticle

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Abstract

Two new vanadium oxide compounds, which contain interlamellar transition metal complexes bound to vanadium oxide sheets, were synthesized hydrothermally. The crystal structure of each reveals unusual coordination geometries and interlayer bonding. [Ni(2,2'-bipyridine)]2[V12O32] (1) was prepared from the reaction of V2O5, NiO, H2O and 2,2'-bipyridyl in the molar ratio 4:8:3312:0.5. The isomorphous compounds [M(2,2'- bipy)]2[V12O32] (where M is Co (1a) and Cu (1b)) were prepared in a similar fashion. The Ni coordination compound 1 crystallizes as amber needles, and the structure was solved in the space group C2/m (12) with unit cell parameters a=24.344(3) Å, b=6.897(3) Å, c= 12.028(2) Å, β=93.60(2)°(R(Rw)=0.039(0.038)). This compound is composed of vanadium(V) oxide layers with nickel atoms coordinated within a single layer via four Ni-O-V linkages. Bidentate bipyridine (bpy) ligands complete the coordination sphere of the nickel atoms and interdigitate via π-π stacking with bpy ligands from the adjacent layer. Cu(en)2[V6O14] (2) crystallizes as black plates in the space group P21/n (14) with unit cell parameters a=8.934(2) Å, b=6.558(1) Å, c=15.694(2) Å, β=99.93(2)°(R(Rw)=0.039(0.035)), from the reaction of CuCl2·2H2O, V2O5, H2O and ethylenediamine in the ratio 1:1:447:4. This structure consists of mixed-valent vanadium(IV,V) oxide sheets forming weak O-Cu bonds to intercalated copper bis(ethylenediamine) complexes.

Original languageEnglish (US)
Pages (from-to)49-60
Number of pages12
JournalJournal of Molecular Structure
Volume470
Issue number1-2
DOIs
StatePublished - Oct 13 1998

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Vanadium
ethylenediamine
Hydrothermal synthesis
Coordination Complexes
Oxides
Transition metals
Crystal structure
2,2'-Dipyridyl
Nickel
Amber
Ligands
Atoms
Needles
Copper
Geometry
vanadium pentoxide

All Science Journal Classification (ASJC) codes

  • Analytical Chemistry
  • Spectroscopy
  • Organic Chemistry
  • Inorganic Chemistry

Cite this

Ollivier, P. J., Deboard, J. R. D., Zapf, P. J., Zubieta, J., Meyer, L. M., Wang, C. C., ... Haushalter, R. C. (1998). Hydrothermal synthesis and crystal structures of two novel vanadium oxides containing interlamellar transition metal complexes. Journal of Molecular Structure, 470(1-2), 49-60. https://doi.org/10.1016/S0022-2860(98)00469-4
Ollivier, Patricia J. ; Deboard, Jeffrey R.D. ; Zapf, Pamela J. ; Zubieta, Jon ; Meyer, Linda M. ; Wang, Chwan Chin ; Mallouk, Thomas E. ; Haushalter, Robert C. / Hydrothermal synthesis and crystal structures of two novel vanadium oxides containing interlamellar transition metal complexes. In: Journal of Molecular Structure. 1998 ; Vol. 470, No. 1-2. pp. 49-60.
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title = "Hydrothermal synthesis and crystal structures of two novel vanadium oxides containing interlamellar transition metal complexes",
abstract = "Two new vanadium oxide compounds, which contain interlamellar transition metal complexes bound to vanadium oxide sheets, were synthesized hydrothermally. The crystal structure of each reveals unusual coordination geometries and interlayer bonding. [Ni(2,2'-bipyridine)]2[V12O32] (1) was prepared from the reaction of V2O5, NiO, H2O and 2,2'-bipyridyl in the molar ratio 4:8:3312:0.5. The isomorphous compounds [M(2,2'- bipy)]2[V12O32] (where M is Co (1a) and Cu (1b)) were prepared in a similar fashion. The Ni coordination compound 1 crystallizes as amber needles, and the structure was solved in the space group C2/m (12) with unit cell parameters a=24.344(3) {\AA}, b=6.897(3) {\AA}, c= 12.028(2) {\AA}, β=93.60(2)°(R(Rw)=0.039(0.038)). This compound is composed of vanadium(V) oxide layers with nickel atoms coordinated within a single layer via four Ni-O-V linkages. Bidentate bipyridine (bpy) ligands complete the coordination sphere of the nickel atoms and interdigitate via π-π stacking with bpy ligands from the adjacent layer. Cu(en)2[V6O14] (2) crystallizes as black plates in the space group P21/n (14) with unit cell parameters a=8.934(2) {\AA}, b=6.558(1) {\AA}, c=15.694(2) {\AA}, β=99.93(2)°(R(Rw)=0.039(0.035)), from the reaction of CuCl2·2H2O, V2O5, H2O and ethylenediamine in the ratio 1:1:447:4. This structure consists of mixed-valent vanadium(IV,V) oxide sheets forming weak O-Cu bonds to intercalated copper bis(ethylenediamine) complexes.",
author = "Ollivier, {Patricia J.} and Deboard, {Jeffrey R.D.} and Zapf, {Pamela J.} and Jon Zubieta and Meyer, {Linda M.} and Wang, {Chwan Chin} and Mallouk, {Thomas E.} and Haushalter, {Robert C.}",
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Ollivier, PJ, Deboard, JRD, Zapf, PJ, Zubieta, J, Meyer, LM, Wang, CC, Mallouk, TE & Haushalter, RC 1998, 'Hydrothermal synthesis and crystal structures of two novel vanadium oxides containing interlamellar transition metal complexes', Journal of Molecular Structure, vol. 470, no. 1-2, pp. 49-60. https://doi.org/10.1016/S0022-2860(98)00469-4

Hydrothermal synthesis and crystal structures of two novel vanadium oxides containing interlamellar transition metal complexes. / Ollivier, Patricia J.; Deboard, Jeffrey R.D.; Zapf, Pamela J.; Zubieta, Jon; Meyer, Linda M.; Wang, Chwan Chin; Mallouk, Thomas E.; Haushalter, Robert C.

In: Journal of Molecular Structure, Vol. 470, No. 1-2, 13.10.1998, p. 49-60.

Research output: Contribution to journalArticle

TY - JOUR

T1 - Hydrothermal synthesis and crystal structures of two novel vanadium oxides containing interlamellar transition metal complexes

AU - Ollivier, Patricia J.

AU - Deboard, Jeffrey R.D.

AU - Zapf, Pamela J.

AU - Zubieta, Jon

AU - Meyer, Linda M.

AU - Wang, Chwan Chin

AU - Mallouk, Thomas E.

AU - Haushalter, Robert C.

PY - 1998/10/13

Y1 - 1998/10/13

N2 - Two new vanadium oxide compounds, which contain interlamellar transition metal complexes bound to vanadium oxide sheets, were synthesized hydrothermally. The crystal structure of each reveals unusual coordination geometries and interlayer bonding. [Ni(2,2'-bipyridine)]2[V12O32] (1) was prepared from the reaction of V2O5, NiO, H2O and 2,2'-bipyridyl in the molar ratio 4:8:3312:0.5. The isomorphous compounds [M(2,2'- bipy)]2[V12O32] (where M is Co (1a) and Cu (1b)) were prepared in a similar fashion. The Ni coordination compound 1 crystallizes as amber needles, and the structure was solved in the space group C2/m (12) with unit cell parameters a=24.344(3) Å, b=6.897(3) Å, c= 12.028(2) Å, β=93.60(2)°(R(Rw)=0.039(0.038)). This compound is composed of vanadium(V) oxide layers with nickel atoms coordinated within a single layer via four Ni-O-V linkages. Bidentate bipyridine (bpy) ligands complete the coordination sphere of the nickel atoms and interdigitate via π-π stacking with bpy ligands from the adjacent layer. Cu(en)2[V6O14] (2) crystallizes as black plates in the space group P21/n (14) with unit cell parameters a=8.934(2) Å, b=6.558(1) Å, c=15.694(2) Å, β=99.93(2)°(R(Rw)=0.039(0.035)), from the reaction of CuCl2·2H2O, V2O5, H2O and ethylenediamine in the ratio 1:1:447:4. This structure consists of mixed-valent vanadium(IV,V) oxide sheets forming weak O-Cu bonds to intercalated copper bis(ethylenediamine) complexes.

AB - Two new vanadium oxide compounds, which contain interlamellar transition metal complexes bound to vanadium oxide sheets, were synthesized hydrothermally. The crystal structure of each reveals unusual coordination geometries and interlayer bonding. [Ni(2,2'-bipyridine)]2[V12O32] (1) was prepared from the reaction of V2O5, NiO, H2O and 2,2'-bipyridyl in the molar ratio 4:8:3312:0.5. The isomorphous compounds [M(2,2'- bipy)]2[V12O32] (where M is Co (1a) and Cu (1b)) were prepared in a similar fashion. The Ni coordination compound 1 crystallizes as amber needles, and the structure was solved in the space group C2/m (12) with unit cell parameters a=24.344(3) Å, b=6.897(3) Å, c= 12.028(2) Å, β=93.60(2)°(R(Rw)=0.039(0.038)). This compound is composed of vanadium(V) oxide layers with nickel atoms coordinated within a single layer via four Ni-O-V linkages. Bidentate bipyridine (bpy) ligands complete the coordination sphere of the nickel atoms and interdigitate via π-π stacking with bpy ligands from the adjacent layer. Cu(en)2[V6O14] (2) crystallizes as black plates in the space group P21/n (14) with unit cell parameters a=8.934(2) Å, b=6.558(1) Å, c=15.694(2) Å, β=99.93(2)°(R(Rw)=0.039(0.035)), from the reaction of CuCl2·2H2O, V2O5, H2O and ethylenediamine in the ratio 1:1:447:4. This structure consists of mixed-valent vanadium(IV,V) oxide sheets forming weak O-Cu bonds to intercalated copper bis(ethylenediamine) complexes.

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