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Title: Hydrothermal synthesis and crystal structure of the Ni{sub 2}(C{sub 4}H{sub 4}N{sub 2})(V{sub 4}O{sub 12})(H{sub 2}O){sub 2} and Ni{sub 3}(C{sub 4}H{sub 4}N{sub 2}){sub 3}(V{sub 8}O{sub 23}) inorganic-organic hybrid compounds. Thermal, spectroscopic and magnetic studies of the hydrated phase

Abstract

Ni{sub 2}(C{sub 4}H{sub 4}N{sub 2})(V{sub 4}O{sub 12})(H{sub 2}O){sub 2}, 1, and Ni{sub 3}(C{sub 4}H{sub 4}N{sub 2}){sub 3}(V{sub 8}O{sub 23}), 2, have been synthesized using mild hydrothermal conditions at 170 deg. C under autogenous pressure. Both phases crystallize in the P-1 triclinic space group, with the unit-cell parameters, a=7.437(7), b=7.571(3), c=7.564(4) A, {alpha}=65.64(4), {beta}=76.09(4), {gamma}=86.25(3){sup o} for 1 and a=8.566(2), b=9.117(2), c=12.619(3) A, {alpha}=71.05(2), {beta}=83.48(4), {gamma}=61.32(3){sup o} for 2, being Z=2 for both compounds. The crystal structure of the three-dimensional 1 is constructed from layers linked between them through the pyrazine molecules. The sheets are formed by edge-shared [Ni{sub 2}O{sub 6}(H{sub 2}O){sub 2}N{sub 2}] nickel(II) dimers octahedra and rings composed by four [V{sub 4}O{sub 12}] vanadium(V) tetrahedra linked through vertices. The crystal structure of 2 is formed from vertex shared [VO{sub 4}] tetrahedra that give rise to twelve member rings. [NiO{sub 4}(C{sub 4}H{sub 4}N{sub 2}){sub 2}]{sub {infinity}} chains, resulting from [NiO{sub 4}N{sub 2}] octahedra and pyrazine molecules, give rise to a 3D skeleton when connecting to [VO{sub 4}] tetrahedra. Diffuse reflectance measurements of 1 indicate a slightly distorted octahedral geometry with values of Dq=880, B=980 and C=2700 cm{sup -1}. Magnetic measurements of 1, carried out in the 5.0-300 K range, indicatemore » the existence of antiferromagnetic couplings with a Neel temperature near to 38 K. - Graphical abstract: Crystal structure of a sheet of Ni{sub 2}(C{sub 4}H{sub 4}N{sub 2})(V{sub 4}O{sub 12})(H{sub 2}O){sub 2}.« less

Authors:
 [1];  [2];  [3];  [3];  [1]
  1. Dpto. de Quimica Inorganica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco, Apdo. 644, E-48080 Bilbao (Spain)
  2. Dpto. de Quimica Inorganica, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco, Apdo. 644, E-48080 Bilbao (Spain), E-mail: joseluis.mesa@ehu.es
  3. Dpto. de Mineralogia y Petrologia, Facultad de Ciencia y Tecnologia, Universidad del Pais Vasco, Apdo. 644, E-48080 Bilbao (Spain)
Publication Date:
OSTI Identifier:
21015758
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 180; Journal Issue: 3; Other Information: DOI: 10.1016/j.jssc.2006.12.037; PII: S0022-4596(07)00018-7; Copyright (c) 2007 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; ANTIFERROMAGNETISM; DIMERS; HYDROTHERMAL SYNTHESIS; LAYERS; NEEL TEMPERATURE; NICKEL COMPOUNDS; PYRAZINES; SPACE GROUPS; TRICLINIC LATTICES; VANADIUM COMPOUNDS

Citation Formats

Larrea, Edurne S., Mesa, Jose L., Pizarro, Jose L., Arriortua, Maria I., and Rojo, Teofilo. Hydrothermal synthesis and crystal structure of the Ni{sub 2}(C{sub 4}H{sub 4}N{sub 2})(V{sub 4}O{sub 12})(H{sub 2}O){sub 2} and Ni{sub 3}(C{sub 4}H{sub 4}N{sub 2}){sub 3}(V{sub 8}O{sub 23}) inorganic-organic hybrid compounds. Thermal, spectroscopic and magnetic studies of the hydrated phase. United States: N. p., 2007. Web. doi:10.1016/j.jssc.2006.12.037.
Larrea, Edurne S., Mesa, Jose L., Pizarro, Jose L., Arriortua, Maria I., & Rojo, Teofilo. Hydrothermal synthesis and crystal structure of the Ni{sub 2}(C{sub 4}H{sub 4}N{sub 2})(V{sub 4}O{sub 12})(H{sub 2}O){sub 2} and Ni{sub 3}(C{sub 4}H{sub 4}N{sub 2}){sub 3}(V{sub 8}O{sub 23}) inorganic-organic hybrid compounds. Thermal, spectroscopic and magnetic studies of the hydrated phase. United States. doi:10.1016/j.jssc.2006.12.037.
Larrea, Edurne S., Mesa, Jose L., Pizarro, Jose L., Arriortua, Maria I., and Rojo, Teofilo. Thu . "Hydrothermal synthesis and crystal structure of the Ni{sub 2}(C{sub 4}H{sub 4}N{sub 2})(V{sub 4}O{sub 12})(H{sub 2}O){sub 2} and Ni{sub 3}(C{sub 4}H{sub 4}N{sub 2}){sub 3}(V{sub 8}O{sub 23}) inorganic-organic hybrid compounds. Thermal, spectroscopic and magnetic studies of the hydrated phase". United States. doi:10.1016/j.jssc.2006.12.037.
@article{osti_21015758,
title = {Hydrothermal synthesis and crystal structure of the Ni{sub 2}(C{sub 4}H{sub 4}N{sub 2})(V{sub 4}O{sub 12})(H{sub 2}O){sub 2} and Ni{sub 3}(C{sub 4}H{sub 4}N{sub 2}){sub 3}(V{sub 8}O{sub 23}) inorganic-organic hybrid compounds. Thermal, spectroscopic and magnetic studies of the hydrated phase},
author = {Larrea, Edurne S. and Mesa, Jose L. and Pizarro, Jose L. and Arriortua, Maria I. and Rojo, Teofilo},
abstractNote = {Ni{sub 2}(C{sub 4}H{sub 4}N{sub 2})(V{sub 4}O{sub 12})(H{sub 2}O){sub 2}, 1, and Ni{sub 3}(C{sub 4}H{sub 4}N{sub 2}){sub 3}(V{sub 8}O{sub 23}), 2, have been synthesized using mild hydrothermal conditions at 170 deg. C under autogenous pressure. Both phases crystallize in the P-1 triclinic space group, with the unit-cell parameters, a=7.437(7), b=7.571(3), c=7.564(4) A, {alpha}=65.64(4), {beta}=76.09(4), {gamma}=86.25(3){sup o} for 1 and a=8.566(2), b=9.117(2), c=12.619(3) A, {alpha}=71.05(2), {beta}=83.48(4), {gamma}=61.32(3){sup o} for 2, being Z=2 for both compounds. The crystal structure of the three-dimensional 1 is constructed from layers linked between them through the pyrazine molecules. The sheets are formed by edge-shared [Ni{sub 2}O{sub 6}(H{sub 2}O){sub 2}N{sub 2}] nickel(II) dimers octahedra and rings composed by four [V{sub 4}O{sub 12}] vanadium(V) tetrahedra linked through vertices. The crystal structure of 2 is formed from vertex shared [VO{sub 4}] tetrahedra that give rise to twelve member rings. [NiO{sub 4}(C{sub 4}H{sub 4}N{sub 2}){sub 2}]{sub {infinity}} chains, resulting from [NiO{sub 4}N{sub 2}] octahedra and pyrazine molecules, give rise to a 3D skeleton when connecting to [VO{sub 4}] tetrahedra. Diffuse reflectance measurements of 1 indicate a slightly distorted octahedral geometry with values of Dq=880, B=980 and C=2700 cm{sup -1}. Magnetic measurements of 1, carried out in the 5.0-300 K range, indicate the existence of antiferromagnetic couplings with a Neel temperature near to 38 K. - Graphical abstract: Crystal structure of a sheet of Ni{sub 2}(C{sub 4}H{sub 4}N{sub 2})(V{sub 4}O{sub 12})(H{sub 2}O){sub 2}.},
doi = {10.1016/j.jssc.2006.12.037},
journal = {Journal of Solid State Chemistry},
number = 3,
volume = 180,
place = {United States},
year = {Thu Mar 15 00:00:00 EDT 2007},
month = {Thu Mar 15 00:00:00 EDT 2007}
}