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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}
}
  • Highlights: {yields} A novel inorganic-organic hybrid vanadate of nickel(II) coordination complex with pyrazine has been synthesized hydrothermally. {yields} The thermal and spectroscopic behavior has been studied. {yields} The compound shows AFM interactions which has been fitted to a magnetic model of lineal chains. -- Abstract: The three-dimensional hybrid compound Ni{sub 3}(C{sub 4}H{sub 4}N{sub 2}){sub 3}(V{sub 8}O{sub 23}) has been synthesized by mild hydrothermal methods under autogenous pressure at 170 {sup o}C. The structure of the phase is stable until 380 {sup o}C. The removal of the pyrazine molecules from the structure induces its collapse. The IR spectrum shows the vibrationmore » modes of the pyrazine molecule and those of the [VO{sub 4}]{sup 3-} groups. A UV-visible spectrum shows the characteristic bands of the Ni(II) d{sup 8}-high-spin cation in a slightly distorted octahedral coordination. Magnetic measurements indicate the existence of antiferromagnetic interactions that can be fitted with a chain model to give g = 2.31, J/k = -5.3, and zJ'/k = -5.5.« less
  • The [M{sub x}{sup II}M{sub 2.5-x}{sup III}(H{sub 2}O){sub 2}(HP{sup III}O{sub 3}){sub y}(P{sup V}O{sub 4}){sub 2-y}F; M=Fe (1), x=2.08, y=1.58; M=Co (2), x=2.5, y=2; Ni (3), x=2.5, y=2] compounds have been synthesized using mild hydrothermal conditions at 170 deg. C during five days. Single-crystals of (1) and (2), and polycrystalline sample of (3) were obtained. These isostructural compounds crystallize in the orthorhombic system, space group Aba2, with a=9.9598(2), b=18.8149(4) and c=8.5751(2) A for (1), a=9.9142(7), b=18.570(1) and c=8.4920(5) A for (2) and a=9.8038(2), b=18.2453(2) and c=8.4106(1) A for (3), with Z=8 in the three phases. An X-ray diffraction study reveals that themore » crystal structure is composed of a three-dimensional skeleton formed by [MO{sub 5}F] and [MO{sub 4}F{sub 2}] (M=Fe, Co and Ni) octahedra and [HPO{sub 3}] tetrahedra, partially substituted by [PO{sub 4}] tetrahedra in phase (1). The IR spectra show the vibrational modes of the water molecules and those of the (HPO{sub 3}){sup 2-} tetrahedral oxoanions. The thermal study indicates that the limit of thermal stability of these phases is 195 deg. C for (1) and 315 deg. C for (2) and (3). The electronic absorption spectroscopy shows the characteristic bands of the Fe(II), Co(II) and Ni(II) high-spin cations in slightly distorted octahedral geometry. Magnetic measurements indicate the existence of global antiferromagnetic interactions between the metallic centers with a ferromagnetic transition in the three compounds at 28, 14 and 21 K for (1), (2) and (3), respectively. Compound (1) exhibits a hysteresis loop with remnant magnetization and coercive field values of 0.72 emu/mol and 880 Oe, respectively. - Abstract: Polyhedral view of the crystal structure of the [M{sub x}{sup II}M{sub 2.5-x}{sup III}(H{sub 2}O){sub 2}(HP{sup III}O{sub 3}){sub y}(P{sup IV}O{sub 4}){sub 2-y}F; M=Fe, x=2.08, y=1.58; M=Co, Ni, x=2.5, y=2] compounds showing the sheets along the [001] direction.« less
  • The organo-templated iron(III) borophosphate (C{sub 3}H{sub 12}N{sub 2})Fe{sup III} {sub 6}(H{sub 2}O){sub 4}[B{sub 4}P{sub 8}O{sub 32}(OH){sub 8}] was prepared under mild hydrothermal conditions (at 443 K) and the crystal structure was determined from single crystal X-ray data at 295 K (monoclinic, P2{sub 1}/c (No. 14), a=5.014(2) A, b=9.309(2) A, c=20.923(7) A, beta=110.29(2){sup o}, V=915.9(5) A{sup 3}, Z=2, R1=0.049, wR2=0.107 for all data, 2234 observed reflections with I>2sigma(I)). The title compound contains a complex inorganic framework of borophosphate trimers [BP{sub 2}O{sub 8}(OH){sub 2}]{sup 5-} together with FeO{sub 4}(OH)(H{sub 2}O)- and FeO{sub 4}(OH){sub 2}-octahedra forming channels with ten-membered ring apertures in whichmore » the diaminopropane cations are located. The magnetization measurements confirm the Fe(III)-state and show an antiferromagnetic ordering at T{sub N}{approx}14.0(1) K. - Graphical abstract: The complex inorganic open-framework of (C{sub 3}H{sub 12}N{sub 2})Fe{sup III} {sub 6}(H{sub 2}O){sub 4}[B{sub 4}P{sub 8}O{sub 32}(OH){sub 8}] consists of borophosphate trimers and iron(III) coordination octahedra arranged to form channels with ten-membered ring apertures in which the organic 1,3-diaminopropane cations are located.« less
  • A hydrothermal reaction of a mixture of cobalt (II) oxalate, phosphorous acid, piperazine and water at 150{sup o}C for 96h followed by heating at 180{sup o}C for 24h gave rise to a new inorganic-organic hybrid solid, [C{sub 4}N{sub 2}H{sub 12}][Co{sub 4}(HPO{sub 3}){sub 2}(C{sub 2}O{sub 4}){sub 3}], I. The structure consists of edge-shared CoO{sub 6} octahedra forming a [Co{sub 2}O{sub 10}] dimers that are connected by HPO{sub 3} and C{sub 2}O{sub 4} units forming a three-dimensional structure with one-dimensional channels. The amine molecules are positioned within these channels. The oxalate units have a dual role of connecting within the plane ofmore » the layer as well as out of the plane. Magnetic susceptibility measurement shows the compound orders antiferromagnetically at low temperature (T{sub N}=22K). Crystal data: I, monoclinic, space group=P2{sub 1}/c (No. 14). a=7.614(15), b=7.514(14), c=17.750(3)A, {beta}=97.351(3){sup o}, V=1007.30(3)A{sup 3}, Z=2, {rho}{sub calc}=2.466g/cm{sup 3}, {mu}{sub (MoK{alpha}}{sub )}=3.496mm{sup -1}, R{sub 1}=0.0310 and wR{sub 2}=0.0807 data [I>2{sigma}(I)].« less
  • The [(C{sub 2}N{sub 2}H{sub 9})VF(PO{sub 4})] compound has been synthesized by hydrothermal techniques under autogeneous pressure at 170 deg. C. The compound was characterized from X-ray powder diffraction data with the Rietveld method. Its crystal structure consists of sheets linked by the ethylenediammonium cations and constructed by chains of VO{sub 3}F{sub 2}N octahedra. The thermal study indicates that the compound is stable up to 290 deg. C. In the IR spectrum the bands of both the ethylenediammonium and phosphate ions are observed. From the reflectance diffuse spectrum the Dq and Racah parameters have been calculated. The magnetic measurements indicate themore » presence of antiferromagnetic interactions.« less