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Title: Synthesis and structures of new niobium cluster compounds with pyridinium cations: (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}].EtOH (Pyr: pyridine, Et: ethyl) and the cubic modification of (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}]

Abstract

Slow crystallization of (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}] from hot ethanol solution affords triclinic (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}].EtOH. Treatment of [Nb{sub 6}Cl{sub 14}(H{sub 2}O){sub 4}].4H{sub 2}O with pyridine in a methanol solution gives the second title compound, the cubic modification of (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}]. Both structures were determined by single crystal X-ray diffraction, (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}].EtOH: P1-bar , a=9.3475(3), b=9.3957(3), c=10.8600(3) A, {alpha}=82.582(1){sup o}, {beta}=78.608(1){sup o}, and {gamma}=78.085(1){sup o}, Z=1, R{sub 1}(F)/wR{sub 2}(F{sup 2})=0.0254/0.0573, cub.-(PyrH){sub 2}[Nb{sub 6}Cl{sub 18}]: Fd3-bar m, a=19.935(2) A, Z=8, R{sub 1}(F)/wR{sub 2}(F{sup 2})=0.0557/0.1796. The cluster compounds contain isolated, molecular [Nb{sub 6}Cl{sup i}{sub 12}Cl{sup a}{sub 6}]{sup 2-} cluster anions with an octahedron of metal atoms edge bridged by chlorido ligands with additional ones on all the six exo positions. These cluster anions are separated by the pyridinium cations and ethanol solvent molecules, respectively. For the cubic modification of (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}], a structural comparison is given to the known rhombohedral modification using the group-subgroup relations as expressed by a Baernighausen tree. - Graphical abstract: The synthesis and structure of a second cubic modification of (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}] and of the new (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}].EtOH are reported, both of which contain isolated niobium halidemore » cluster anions with an octahedral core of metal atoms.« less

Authors:
;  [1];  [2]
  1. Institut fuer Chemie, Abteilung Anorganische Chemie/Festkoerperchemie, Universitaet Rostock, Albert-Einstein-Str. 3a, Rostock D-18059 (Germany)
  2. Institut fuer Chemie, Abteilung Anorganische Chemie/Festkoerperchemie, Universitaet Rostock, Albert-Einstein-Str. 3a, Rostock D-18059 (Germany), E-mail: Martin.Koeckerling@uni-rostock.de
Publication Date:
OSTI Identifier:
21212046
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 181; Journal Issue: 10; Other Information: DOI: 10.1016/j.jssc.2008.06.038; PII: S0022-4596(08)00336-8; Copyright (c) 2008 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ANIONS; CATIONS; CRYSTALLIZATION; CUBIC LATTICES; ETHANOL; LIGANDS; METHANOL; MONOCRYSTALS; NIOBIUM CHLORIDES; NIOBIUM COMPLEXES; PYRIDINE; SYNTHESIS; TRICLINIC LATTICES; X-RAY DIFFRACTION

Citation Formats

Flemming, Anke, Hoppe, Alessandra, and Koeckerling, Martin. Synthesis and structures of new niobium cluster compounds with pyridinium cations: (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}].EtOH (Pyr: pyridine, Et: ethyl) and the cubic modification of (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}]. United States: N. p., 2008. Web. doi:10.1016/j.jssc.2008.06.038.
Flemming, Anke, Hoppe, Alessandra, & Koeckerling, Martin. Synthesis and structures of new niobium cluster compounds with pyridinium cations: (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}].EtOH (Pyr: pyridine, Et: ethyl) and the cubic modification of (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}]. United States. doi:10.1016/j.jssc.2008.06.038.
Flemming, Anke, Hoppe, Alessandra, and Koeckerling, Martin. Wed . "Synthesis and structures of new niobium cluster compounds with pyridinium cations: (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}].EtOH (Pyr: pyridine, Et: ethyl) and the cubic modification of (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}]". United States. doi:10.1016/j.jssc.2008.06.038.
@article{osti_21212046,
title = {Synthesis and structures of new niobium cluster compounds with pyridinium cations: (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}].EtOH (Pyr: pyridine, Et: ethyl) and the cubic modification of (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}]},
author = {Flemming, Anke and Hoppe, Alessandra and Koeckerling, Martin},
abstractNote = {Slow crystallization of (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}] from hot ethanol solution affords triclinic (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}].EtOH. Treatment of [Nb{sub 6}Cl{sub 14}(H{sub 2}O){sub 4}].4H{sub 2}O with pyridine in a methanol solution gives the second title compound, the cubic modification of (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}]. Both structures were determined by single crystal X-ray diffraction, (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}].EtOH: P1-bar , a=9.3475(3), b=9.3957(3), c=10.8600(3) A, {alpha}=82.582(1){sup o}, {beta}=78.608(1){sup o}, and {gamma}=78.085(1){sup o}, Z=1, R{sub 1}(F)/wR{sub 2}(F{sup 2})=0.0254/0.0573, cub.-(PyrH){sub 2}[Nb{sub 6}Cl{sub 18}]: Fd3-bar m, a=19.935(2) A, Z=8, R{sub 1}(F)/wR{sub 2}(F{sup 2})=0.0557/0.1796. The cluster compounds contain isolated, molecular [Nb{sub 6}Cl{sup i}{sub 12}Cl{sup a}{sub 6}]{sup 2-} cluster anions with an octahedron of metal atoms edge bridged by chlorido ligands with additional ones on all the six exo positions. These cluster anions are separated by the pyridinium cations and ethanol solvent molecules, respectively. For the cubic modification of (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}], a structural comparison is given to the known rhombohedral modification using the group-subgroup relations as expressed by a Baernighausen tree. - Graphical abstract: The synthesis and structure of a second cubic modification of (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}] and of the new (PyrH){sub 2}[Nb{sub 6}Cl{sub 18}].EtOH are reported, both of which contain isolated niobium halide cluster anions with an octahedral core of metal atoms.},
doi = {10.1016/j.jssc.2008.06.038},
journal = {Journal of Solid State Chemistry},
number = 10,
volume = 181,
place = {United States},
year = {Wed Oct 15 00:00:00 EDT 2008},
month = {Wed Oct 15 00:00:00 EDT 2008}
}