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Title: Synthesis and structural characterization of Al{sub 4}Si{sub 2}C{sub 5}-homeotypic aluminum silicon oxycarbide, (Al{sub 6-x}Si{sub x})(O{sub y}C{sub 5-y}) (x{approx}0.8 and y{approx}1.6)

Abstract

We have prepared a new layered oxycarbide, [Al{sub 5.25(5)}Si{sub 0.75(5)}][O{sub 1.60(7)}C{sub 3.40(7)}], by isothermal heating of (Al{sub 4.4}Si{sub 0.6})(O{sub 1.0}C{sub 3.0}) at 2273 K near the carbon-carbon monoxide buffer. The crystal structure was characterized using X-ray powder diffraction, transmission electron microscopy and energy dispersive X-ray spectroscopy (EDX). The title compound is trigonal with space group R3m (centrosymmetric), Z=3, and hexagonal cell dimensions a=0.32464(2) nm, c=4.00527(14) nm and V=0.36556(3) nm{sup 3}. The atom ratios Al:Si were determined by EDX, and the initial structural model was derived by the direct methods. The final structural model showed the positional disordering of one of the three types of Al/Si sites. The reliability indices were R{sub wp}=4.45% (S=1.30), R{sub p}=3.48%, R{sub B}=2.27% and R{sub F}=1.25%. The crystal is composed of three types of domains with nearly the same fraction, one of which has the crystal structure of space group R3-bar m. The crystal structure of the remaining two domains, which are related by pseudo-symmetry inversion, is noncentrosymmetric with space group R3m. - Graphical Abstract: A new aluminum silicon oxycarbide, (Al{sub 6-x}Si{sub x})(O{sub y}C{sub 5-y}) (x{approx}0.8 and y{approx}1.6). The crystal is composed of three types of domains (I, II and III), and hence the structure ismore » represented by a split-atom model. Individual crystal structures can be regarded as layered structures, which consist of A-type [(Al,Si){sub 4}(O,C){sub 4}] unit layers and B-type [(Al,Si)(O,C){sub 2}] single layers.« less

Authors:
; ; ;  [1];  [2];  [1]
  1. Department of Environmental and Materials Engineering, Nagoya Institute of Technology, Nagoya 466-8555 (Japan)
  2. Cooperative Research Facility Center, Toyohashi University of Technology, Toyohashi 441-8580 (Japan)
Publication Date:
OSTI Identifier:
21483674
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Solid State Chemistry; Journal Volume: 183; Journal Issue: 9; Other Information: DOI: 10.1016/j.jssc.2010.07.031; PII: S0022-4596(10)00313-0; Copyright (c) 2010 Elsevier Science B.V., Amsterdam, The Netherlands, All rights reserved.
Country of Publication:
United States
Language:
English
Subject:
36 MATERIALS SCIENCE; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ALUMINIUM COMPOUNDS; CARBON; CARBON MONOXIDE; DOMAIN STRUCTURE; HEATING; LATTICE PARAMETERS; LAYERS; ORGANIC OXYGEN COMPOUNDS; SILICON COMPOUNDS; SPACE GROUPS; STRUCTURAL MODELS; SYNTHESIS; TRANSMISSION ELECTRON MICROSCOPY; TRIGONAL LATTICES; X-RAY DIFFRACTION; X-RAY SPECTROSCOPY; CARBON COMPOUNDS; CARBON OXIDES; CHALCOGENIDES; COHERENT SCATTERING; CRYSTAL LATTICES; CRYSTAL STRUCTURE; DIFFRACTION; ELECTRON MICROSCOPY; ELEMENTS; MICROSCOPY; NONMETALS; ORGANIC COMPOUNDS; OXIDES; OXYGEN COMPOUNDS; SCATTERING; SPECTROSCOPY; SYMMETRY GROUPS

Citation Formats

Kaga, Motoaki, Urushihara, Daisuke, Iwata, Tomoyuki, Sugiura, Keita, Nakano, Hiromi, and Fukuda, Koichiro, E-mail: fukuda.koichiro@nitech.ac.j. Synthesis and structural characterization of Al{sub 4}Si{sub 2}C{sub 5}-homeotypic aluminum silicon oxycarbide, (Al{sub 6-x}Si{sub x})(O{sub y}C{sub 5-y}) (x{approx}0.8 and y{approx}1.6). United States: N. p., 2010. Web. doi:10.1016/j.jssc.2010.07.031.
Kaga, Motoaki, Urushihara, Daisuke, Iwata, Tomoyuki, Sugiura, Keita, Nakano, Hiromi, & Fukuda, Koichiro, E-mail: fukuda.koichiro@nitech.ac.j. Synthesis and structural characterization of Al{sub 4}Si{sub 2}C{sub 5}-homeotypic aluminum silicon oxycarbide, (Al{sub 6-x}Si{sub x})(O{sub y}C{sub 5-y}) (x{approx}0.8 and y{approx}1.6). United States. doi:10.1016/j.jssc.2010.07.031.
Kaga, Motoaki, Urushihara, Daisuke, Iwata, Tomoyuki, Sugiura, Keita, Nakano, Hiromi, and Fukuda, Koichiro, E-mail: fukuda.koichiro@nitech.ac.j. Wed . "Synthesis and structural characterization of Al{sub 4}Si{sub 2}C{sub 5}-homeotypic aluminum silicon oxycarbide, (Al{sub 6-x}Si{sub x})(O{sub y}C{sub 5-y}) (x{approx}0.8 and y{approx}1.6)". United States. doi:10.1016/j.jssc.2010.07.031.
@article{osti_21483674,
title = {Synthesis and structural characterization of Al{sub 4}Si{sub 2}C{sub 5}-homeotypic aluminum silicon oxycarbide, (Al{sub 6-x}Si{sub x})(O{sub y}C{sub 5-y}) (x{approx}0.8 and y{approx}1.6)},
author = {Kaga, Motoaki and Urushihara, Daisuke and Iwata, Tomoyuki and Sugiura, Keita and Nakano, Hiromi and Fukuda, Koichiro, E-mail: fukuda.koichiro@nitech.ac.j},
abstractNote = {We have prepared a new layered oxycarbide, [Al{sub 5.25(5)}Si{sub 0.75(5)}][O{sub 1.60(7)}C{sub 3.40(7)}], by isothermal heating of (Al{sub 4.4}Si{sub 0.6})(O{sub 1.0}C{sub 3.0}) at 2273 K near the carbon-carbon monoxide buffer. The crystal structure was characterized using X-ray powder diffraction, transmission electron microscopy and energy dispersive X-ray spectroscopy (EDX). The title compound is trigonal with space group R3m (centrosymmetric), Z=3, and hexagonal cell dimensions a=0.32464(2) nm, c=4.00527(14) nm and V=0.36556(3) nm{sup 3}. The atom ratios Al:Si were determined by EDX, and the initial structural model was derived by the direct methods. The final structural model showed the positional disordering of one of the three types of Al/Si sites. The reliability indices were R{sub wp}=4.45% (S=1.30), R{sub p}=3.48%, R{sub B}=2.27% and R{sub F}=1.25%. The crystal is composed of three types of domains with nearly the same fraction, one of which has the crystal structure of space group R3-bar m. The crystal structure of the remaining two domains, which are related by pseudo-symmetry inversion, is noncentrosymmetric with space group R3m. - Graphical Abstract: A new aluminum silicon oxycarbide, (Al{sub 6-x}Si{sub x})(O{sub y}C{sub 5-y}) (x{approx}0.8 and y{approx}1.6). The crystal is composed of three types of domains (I, II and III), and hence the structure is represented by a split-atom model. Individual crystal structures can be regarded as layered structures, which consist of A-type [(Al,Si){sub 4}(O,C){sub 4}] unit layers and B-type [(Al,Si)(O,C){sub 2}] single layers.},
doi = {10.1016/j.jssc.2010.07.031},
journal = {Journal of Solid State Chemistry},
number = 9,
volume = 183,
place = {United States},
year = {Wed Sep 15 00:00:00 EDT 2010},
month = {Wed Sep 15 00:00:00 EDT 2010}
}
  • A new aluminum silicon oxycarbonitride, (Al{sub 5.8}Si{sub 1.2})(O{sub 1.0}C{sub 3.5}N{sub 1.5}), has been synthesized and characterized by X-ray powder diffraction (XRPD), transmission electron microscopy (TEM), energy dispersive X-ray spectroscopy (EDX) and electron energy loss spectroscopy (EELS). The title compound is hexagonal with space group P6{sub 3}/mmc and unit-cell dimensions a=0.322508(4) nm, c=3.17193(4) nm and V=0.285717(6) nm{sup 3}. The atom ratios of Al:Si and those of O:C:N were, respectively, determined by EDX and EELS. The initial structural model was successfully derived from the XRPD data by the direct methods and further refined by the Rietveld method. The crystal is most probablymore » composed of four types of domains with nearly the same fraction, each of which is isotypic to Al{sub 7}C{sub 3}N{sub 3} with space group P6{sub 3}mc. The existence of another new oxycarbonitride (Al{sub 6.6}Si{sub 1.4})(O{sub 0.7}C{sub 4.3}N{sub 2.0}), which must be homeotypic to Al{sub 8}C{sub 3}N{sub 4}, has been also demonstrated by XRPD and TEM. - Graphical abstract: A new oxycarbonitride discovered in the Al-Si-O-C-N system, (Al{sub 7-x}Si{sub x})(O{sub y}C{sub z}N{sub 6-y-z}) (x{approx}1.2, y{approx}1.0 and z{approx}3.5). The crystal is composed of four types of domains (I, II, III and IV), and hence the structure is represented by a split-atom model. Individual crystal structures can be regarded as layered structures, which consist of A-type [(Al, Si){sub 4}(O, C, N){sub 4}] unit layers and B-type [(Al, Si)(O, C, N){sub 2}] single layers. Highlights: > (Al{sub 5.8}Si{sub 1.2})(O{sub 1.0}C{sub 3.5}N{sub 1.5}) as a new aluminum silicon oxycarbonitride. > Crystal structure is determined and represented by a split-atom model. > Existence of another new oxycarbonitride (Al{sub 6.6}Si{sub 1.4})(O{sub 0.7}C{sub 4.3}N{sub 2.0}) is demonstrated. > Both new materials are formed by oxidation and nitridation of (Al, Si){sub 6}(O, C){sub 5}.« less
  • A new quaternary layered oxycarbide, [Al{sub 4.39(5)}Si{sub 0.61(5)}]{sub S}IGMA{sub 5}[O{sub 1.00(2)}C{sub 2.00(2)}]{sub S}IGMA{sub 3}C, has been synthesized and characterized by X-ray powder diffraction, transmission electron microscopy and energy dispersive X-ray spectroscopy (EDX). The title compound was found to be hexagonal with space group P6{sub 3}/mmc, Z=2, and unit-cell dimensions a=0.32783(1) nm, c=2.16674(7) nm and V=0.20167(1) nm{sup 3}. The atom ratios Al:Si were determined by EDX, and the initial structural model was derived by the direct methods. The final structural model showed the positional disordering of one of the three types of Al/Si sites. The maximum-entropy methods-based pattern fitting (MPF) methodmore » was used to confirm the validity of the split-atom model, in which conventional structure bias caused by assuming intensity partitioning was minimized. The reliability indices calculated from the MPF were R{sub wp}=3.73% (S=1.20), R{sub p}=2.94%, R{sub B}=1.04% and R{sub F}=0.81%. The crystal was an inversion twin. Each twin-related individual was isostructural with Al{sub 4}SiC{sub 4} (space group P6{sub 3}mc, Z=2). - Graphical abstract: A new oxycarbide discovered in the Al-Si-O-C system, Al{sub 4}SiC{sub 4}-homeotypic [Al{sub 4.4}Si{sub 0.6}][O{sub 1.0}C{sub 2.0}]C. The crystal is an inversion twin, and hence the structure is represented by a split-atom model. The three-dimensional electron density distributions are determined by the maximum-entropy methods-based pattern fitting, being consistent with the disordered structural model.« less
  • The reactions of ammonium perrhenate, HCl(aq), and the phosphinothiol ligands (2-HSC{sub 6}H{sub 4})P(C{sub 6}H{sub 4}X){sub 2}, where X = H or SH [abbreviated P-(SH){sub x} (x = 1, 3)], in alcohol have led to the isolation of a series of rhenium complexes containing the [M(P{minus}S{sub x}){sub 2}] core, represented by [Re[P(C{sub 6}H{sub 4}S){sub 3}] [P(C{sub 6}H{sub 4}S){sub 2}(C{sub 6}H{sub 4}SH)]] (1), [ReOCl-[OP(C{sub 6}H{sub 5}){sub 2}(C{sub 6}H{sub 4}S)][P(C{sub 6}H{sub 5}){sub 2}(C{sub 6}H{sub 4}S)]] (3), and [ReOCl[OP(C{sub 6}H{sub 5}){sub 2}(2-SC{sub 6}H{sub 3}-3-SiMe{sub 3})]{sub 2}] (5). The reaction of 1 with NEt{sub 3}results in the formation of [HNEt{sub 3}][Re[P(C{sub 6}H{sub 4}S){sub 3}]{sub 2}]more » (2) by deprotonation of a thiol ligand. The reaction of ammonium perrhenate with P-(SH) also led to the isolation of the binuclear species [ReOCl[OP(C{sub 6}H{sub 5}){sub 2}(2-SC{sub 6}H{sub 3}-3-SiMe{sub 3})]{sub 2}] (4). Crystal data are given.« less
  • The reactions of the cis-dioxorhenium(VII)-catecholate complex [(CH{sub 3}CH{sub 2}){sub 4}N][ReO{sub 2}(O{sub 2}C{sub 6}H{sub 4}){sub 2}] (1) with either monosubstituted organohydrazines (C{sub 6}H{sub 5}NHNH{sub 2}; 4-BrC{sub 6}H{sub 4}NHNH{sub 2}) or 1,1 disubstituted organohydrazines (Ph{sub 2-}NNH{sub 2}) yield the cis-bis(diazenido) core complexes [(CH{sub 3}CH{sub 2}){sub 4}N][Re(NNR){sub 2}(O{sub 2}C{sub 6}H{sub 4}){sub 2}] (5, R = C{sub 6}H{sub 5}; 6, R = 4-BrC{sub 6}H{sub 4}) and the cis-bis(hydrazido) core species [(CH{sub 3}CH{sub 2}){sub 4}N][Re(NNPh{sub 2}){sub 2}(O{sub 2}C36H{sub 4}){sub 2}(O{sub 2}C36H{sub 4}){sub 2}] (7). Elution of 5 in a 3:1 mixture of toluene/methanol on a column of silica gel resulted in cation exchange to givemore » Na[Re(NNPh){sub 2}-(O{sub 2}C{sub 6}H{sub 4}){sub 2}]{center_dot}CH{sub 3}CN (8) as a one-dimensional polymer ([Na(CH{sub 3}CN)]{sup +}[Re(NNPh){sub 2}(O{sub 2}C{sub 6}H{sub 4}){sub 2}]{sup {minus}}){sub 2}. Crystal data for C{sub 32}H{sub 38}N{sub 5}O{sub 4}Re (5): P2{sub 1}/c,a = 14.458(3) {angstrom}, b = 10.436(2) {angstrom}, c = 21.767(4) {angstrom}, {beta} = 107.04(3){degrees}, V = 3140(2) {angstrom}{sup 3}, Z = 4, D {sub calc} = 1.572 g cm{sup {minus}3}; structure solution and refinement based on 3256 reflections with I{sub o} {ge} 3{sigma}(I{sub o}) converged at R = 0.053. Crystal data for C{sub 44}H{sub 48}N{sub 5}O{sub 4}Re (7): P1, a = 11.660(2) {angstrom}, b = 11.864(2) {angstrom}, c = 15.400(2) {angstrom}, {alpha} = 107.12(3){degrees}, {beta} = 94.99(3){degrees}, {gamma} = 97.61(3){degrees}, V = 2000(1) {angstrom}{sup 3}, Z = 2, D{sub calc} = 1.490 g cm{sup {minus}3}; 3702 reflections, R = 0.0534. Crystal data for C{sub 26}H{sub 18}N{sub 5}NaO{sub 4}Re (8): P2/n, a = 5.785(1) {angstrom}, b = 9.670(2) {angstrom}, c = 23.142(5) {angstrom}. {beta} = 90.91(30)degrees, V = 1294.4(7) {angstrom}{sup 3}, Z = 2, D{sub calc} = 1.737 g cm{sup {minus}3}; 1517 reflections, R = 0.049.« less
  • Technetium(III) complexes of the general formula cis(Cl),trans(P)-(TcCl{sub 2}(P){sub 2}L){sup +}, where (P) is dimethylphenylphosphine (PMe{sub 2}Ph) or ethyldiphenylphosphine (PEtPh{sub 2}) and L is 2,2{prime}-bipyridine (bpy), 4,4{prime}-dimethyl-2,2{prime}-bipyridine (Me{sub 2}bpy), or 1,10-phenanthroline (phen), have been synthesized and characterized. They are prepared by L substitution onto, with concomitant displacement of one chloride and one phosphine ligand from, the mer-TcCl{sub 3}(P){sub 3} starting material in refluxing ethanol. Analysis of these complexes by fast atom bombardment mass spectrometry (in the positive ion mode) provides fingerprint mass spectra that exhibit peaks assigned to the molecular ion M{sup +} as well as peaks assigned to M{sup +}more » minus one or more monodentate ligands. Results of single-crystal x-ray structure determinations of cis(Cl),trans(P)-(TcCl{sub 2}(PMe{sub 2}Ph){sub 2}(bpy))BPh{sub 4} (A), cis(Cl),trans(P)-(TcCl{sub 2{minus}} (PMe{sub 2}Ph){sub 2}(phen))BPh{sub 4} (B), and cis(Cl),trans(P)-(TcCl{sub 2}(PEtPh{sub 2}){sub 2}(bpy))SO{sub 3}CF{sub 3} (C), with formula weights of 921.62, 945.64, and 903.65, respectively are reported. 26 refs., 5 figs., 5 tabs.« less