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Title: Hydrothermal synthesis, crystal structure, and magnetic properties of a novel 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}]

Abstract

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 which 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.

Authors:
 [1];  [2]; ; ;  [1];  [1]
  1. Max-Planck-Institut fuer Chemische Physik fester Stoffe, Noethnitzer Strasse 40, 01187 Dresden (Germany)
  2. (China)
Publication Date:
OSTI Identifier:
21370357
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 182; Journal Issue: 4; Other Information: DOI: 10.1016/j.jssc.2009.01.012; PII: S0022-4596(09)00020-6; Copyright (c) 2009 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; ANTIFERROMAGNETISM; BORON PHOSPHATES; HYDROTHERMAL SYNTHESIS; IRON COMPOUNDS; MAGNETIC PROPERTIES; MAGNETIZATION; MONOCLINIC LATTICES; TEMPERATURE RANGE 0273-0400 K; BORON COMPOUNDS; CRYSTAL LATTICES; CRYSTAL STRUCTURE; MAGNETISM; OXYGEN COMPOUNDS; PHOSPHATES; PHOSPHORUS COMPOUNDS; PHYSICAL PROPERTIES; SYNTHESIS; TEMPERATURE RANGE; TRANSITION ELEMENT COMPOUNDS

Citation Formats

Huang Yaxi, Department of Materials Science and Engineering, College of Materials, Xiamen University, 361005 Xiamen, Schnelle, Walter, Zhang Hui, Borrmann, Horst, and Kniep, Ruediger, E-mail: kniep@cpfs.mpg.d. Hydrothermal synthesis, crystal structure, and magnetic properties of a novel 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}]. United States: N. p., 2009. Web. doi:10.1016/j.jssc.2009.01.012.
Huang Yaxi, Department of Materials Science and Engineering, College of Materials, Xiamen University, 361005 Xiamen, Schnelle, Walter, Zhang Hui, Borrmann, Horst, & Kniep, Ruediger, E-mail: kniep@cpfs.mpg.d. Hydrothermal synthesis, crystal structure, and magnetic properties of a novel 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}]. United States. doi:10.1016/j.jssc.2009.01.012.
Huang Yaxi, Department of Materials Science and Engineering, College of Materials, Xiamen University, 361005 Xiamen, Schnelle, Walter, Zhang Hui, Borrmann, Horst, and Kniep, Ruediger, E-mail: kniep@cpfs.mpg.d. 2009. "Hydrothermal synthesis, crystal structure, and magnetic properties of a novel 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}]". United States. doi:10.1016/j.jssc.2009.01.012.
@article{osti_21370357,
title = {Hydrothermal synthesis, crystal structure, and magnetic properties of a novel 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}]},
author = {Huang Yaxi and Department of Materials Science and Engineering, College of Materials, Xiamen University, 361005 Xiamen and Schnelle, Walter and Zhang Hui and Borrmann, Horst and Kniep, Ruediger, E-mail: kniep@cpfs.mpg.d},
abstractNote = {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 which 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.},
doi = {10.1016/j.jssc.2009.01.012},
journal = {Journal of Solid State Chemistry},
number = 4,
volume = 182,
place = {United States},
year = 2009,
month = 4
}
  • The utilization of the hydrothermal technique in combination with cationic organic templates has been extensively used in the synthesis of zeolites and molecular sieves. Here, the authors report the hydrothermal synthesis and single-crystal structure of (H{sub 3}N(CH{sub 2}){sub 3}NH{sub 3})[V{sub 4}O{sub 10}], a layered mixed-valence vanadium oxide with organic ammonium cations between the layers. 21 refs., 4 figs.
  • A new manganese(II) phosphate templated by ethylenediamine, (C{sub 2}H{sub 10}N{sub 2})[Mn{sub 2}(HPO{sub 4}){sub 3}(H{sub 2}O)], has been prepared by hydrothermal synthesis and characterized by single-crystal diffraction data and spectroscopic and magnetic techniques. The compound crystallizes in the monoclinic space group P2{sub 1}/n with a = 21.961(7), b = 9.345(1), c = 6.639(2) {angstrom}; {beta} = 91.06(2){degree}; V = 1362.3(6) {angstrom}{sup 3}; and Z = 4. The structure consists of anionic sheets of formula [Mn{sub 2}(HPO{sub 4}){sub 3}]{sup 2-}, being the charge compensated by ethylendiammonium cations. The sheets are constructed by edge-sharing MnO{sub 6} octahedra, MnO{sub 5} trigonal bipyramids, and hydrogenmore » phosphate tetrahedra. Within a layer, the edge-sharing octahedra and the trigonal bipyramids are linked in an alternating way, forming zigzag chains along the [001] direction. The ethylenediammonium cations and the water molecules are located in the interlayer space. The compound has been characterized by IR spectroscopy. A study of the compound by luminescence and diffuse reflectance spectroscopies is carried out. The Dq and Racah parameters have been calculated for Mn(II) ions in octahedral sites. The EST spectra at different temperatures of the compound show isotropic signals, with a g value that remains unchanged with variation in temperature. The intensity and the line width of the ESR signals increase continuously from room temperature to 4.2 K. Magnetic measurements from room temperature to 1.8 K indicate the presence of antiferromagnetic interactions. A value of J/k = {minus}0.75 K for the exchange parameter has been calculated by fitting the experimental magnetic data to a triangular lattice antiferromagnet of S = 5/2 spins.« less
  • Two new fluoro-vanadyl-hydrogenarsenate compounds templated by ethylenediamine and piperazine with formula, (C{sub 2}N{sub 2}H{sub 10}){sub 0.5}[(VO)(HAsO{sub 4})F] (1) and (C{sub 4}N{sub 2}H{sub 12}){sub 0.5}[(VO)(HAsO{sub 4})F] (2), respectively, have been synthesized by using mild hydrothermal conditions under autogenous pressure. The crystal structures have been solved from single-crystal X-ray diffraction data. The phases crystallize in the P2{sub 1}/c monoclinic space group with the unit-cell parameters a=7.8634(4) A, b=7.7658(4) A, c=10.4195(6) A, {beta}=101.524(5){sup o} for compound (1) and a=6.301(1) A, b=10.244(1) A, c=10.248(1) A and {beta}=95.225(1){sup o} for compound (2). These phases exhibit a layered inorganic framework. In both cases, the structure ismore » built from secondary building units (SBU) which are formed by [V{sub 2}O{sub 8}F{sub 2}] edge-shared dimeric vanadyl octahedra, connected by the vertices to two hydrogenarsenate tetrahedra. The repetition of this SBU unit originates sheets along the [1 0 0] direction. The ethylenediammonium and piperazinium cations are located inside the interlayer space. The limit of thermal stability for compounds (1) and (2) is, approximately, 250 and 230 deg. C, respectively. Near this temperature, both phases loose their organic cations and the fluoride anions. The diffuse reflectance spectra confirm the presence of vanadyl ions, in which the vanadium(IV) cations have a d{sup 1} electronic configuration in a slightly distorted octahedral environment. ESR spectra of both phases are isotropic with mean g-values of 1.93 and 1.96 for ethylendiamine and piperazine phases, respectively. Magnetic measurements for (1) and (2) indicate the existence of antiferromagnetic exchange couplings. - Graphical abstract: Polyhedral view of the layered crystal structure of (C{sub 2}H{sub 10}N{sub 2}){sub 0.5} [(VO)(HAsO{sub 4})F].« less
  • A novel cobalt borophosphate, (NH{sub 4}){sub 2}(C{sub 4}H{sub 12}N{sub 2})[Co{sub 2}B{sub 4}P{sub 6}O{sub 24}(OH){sub 2}].H{sub 2}O with the mixed cations has been synthesized under mild hydrothermal conditions. Its crystal structure was determined by the single-crystal X-ray diffraction (tetragonal, I4{sub 1}/a (no. 88), a=14.207(3) A, c=24.956(6) A, V=5037.09(2) A{sup 3}, Z=8). The crystal structure consists of a new type of three-dimensional borophosphatic anionic partial framework, which is built from the condensation of the fundamental building unit (FBU) [B{sub 2}P{sub 3}O{sub 14}(OH)]. The CoO{sub 6} octahedra are enchased in such borophosphate network to form a complex open framework with a three-dimensional intersectingmore » channel system, the voids of which are occupied by ammonium, dipronated piperazine ions and water molecules, respectively. The magnetic measurement of the title compound has also been investigated. - Graphical abstract: A new organically-templated cobalt borophosphate, (NH{sub 4}){sub 2}(C{sub 4}H{sub 12}N{sub 2})[Co{sub 2}B{sub 4}P{sub 6}O{sub 24}(OH){sub 2}].H{sub 2}O with a novel borophosphate 3D anionic partial framework has been synthesized under mild hydrothermal conditions. Highlights: > The first cobalt borophosphate with the 3D anionic partial borophosphate network. > A porous framework with an intersecting three-dimensional channel system. > The borophosphate compound with the mixed cations.« less
  • A coordination iron phosphate, Fe(phen)(HPO{sub 4})(H{sub 2}PO{sub 4}).0.5H{sub 2}O (I), has been hydrothermally synthesized and characterized by elemental analysis, IR spectral analysis, thermogravimetric analysis, and single-crystal X-ray diffraction. The title compound crystallizes in the monoclinic system, space group C2/m (No. 12), with cell parameters M=438.03, a=21.421(5)A, b=6.4292(1)A, c=12.190(3)A, {beta}=105.964(9){sup o}, V=1614.1(6)A{sup 3}, Z=4, R1[I>2{sigma}(I)]=0.0545, wR2[I>2{sigma}(I)]=0.1186. This compound displays a new structure of ladder-like chains, in which each one-dimensional chain is constituted by the distorted octahedral units of Fe{sup 3+} bridged through PO{sub 4} tetrahedron. The phen ligands in the compound bind in a bidentate fashion to the metal atoms andmore » the ladder-like structure of the compound extends into a three-dimensional supramolecular array via {pi}-{pi} stacking interactions of phen ligands. Mossbauer spectroscopy shows the presence of Fe{sup 3+} in the octahedral coordination. Magnetic susceptibility measurement studies show that this material may model as anti-ferromagnetic.« less