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Double (n = 2) and triple (n = 3) [M4Bi2n-2O2n]x+ polycationic ribbons in the new Bi∼3Cd∼3.72M∼1.28O5(PO4)3 oxyphosphate (M=Co, Cu, Zn)

Identifieur interne : 000232 ( PascalFrancis/Checkpoint ); précédent : 000231; suivant : 000233

Double (n = 2) and triple (n = 3) [M4Bi2n-2O2n]x+ polycationic ribbons in the new Bi∼3Cd∼3.72M∼1.28O5(PO4)3 oxyphosphate (M=Co, Cu, Zn)

Auteurs : Marie Colmont [France] ; Marielle Huve [France] ; El Mostafa Ketatni [Maroc] ; Francis Abraham [France] ; Olivier Mentre [France]

Source :

RBID : Pascal:04-0016354

Descripteurs français

English descriptors

Abstract

The crystal structure of the new Bi∼3Cd∼3.72Co∼1.28O5(PO4)3 has been refined from single crystal XRD data, R1 = 5.37%, space group Abmm, a = 11.5322(28) Å, b = 5.4760(13) Å, c = 23.2446(56) Å, Z = 4. Compared to Bi∼1.2M∼1.2O1.5(PO4) and Bi∼6.2Cu∼6.2O8(PO4)5, this compound is an additional example of disordered Bi3+/M2+ oxyphosphate and is well described from the arrangement of double [Bi4Cd4O6]8+ (= D) and triple [Bi2Cd3.44Co0.56O4]6+ (= T) polycationic ribbons formed of edge-sharing O(Bi,M)4 tetrahedra surrounded by PO4 groups. According to the nomenclature defined in this work, the sequence is TT/DtDt, where t stands for the tunnels created by PO4 between two subsequent double ribbons and occupied by Co2+. The HREM study allows a clear visualization of the announced sequence by comparison with the refined crystal structure. The Bi3+ / M2+ statistic disorder at the edges of T and D entities is responsible for the PO4 multi-configuration disorder around a central P atom. Infrared spectroscopy and neutron diffraction of similar compounds (without the highly absorbing Cadmium) even suggests the long range ordering loss for phosphates. Therefore, electron diffraction shows the existence of a modulation vector q* = 1/2a* + (1/3 + ε)b* which pictures cationic ordering in the (001) plane, at the crystallite scale. This ordering is largely lost at the single crystal scale. The existence of mixed Bi3+/M2+ positions also enables a partial filling of the tunnels by Co2+ and yields a composition range checked by solid state reaction. The title compound can be prepared as a single phase and also the M = Zn2+ term can be obtained in a biphasic mixture. For M = Cu2+, a monoclinic distortion has been evidenced from XRD and HREM patterns but surprisingly, the orthorhombic ideal form can also be obtained in similar conditions.


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Pascal:04-0016354

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Bi
<sub>2n-2</sub>
O
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]
<sup>x+</sup>
polycationic ribbons in the new Bi
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Cd
<sub>∼3.72</sub>
M
<sub>∼1.28</sub>
O
<sub>5</sub>
(PO
<sub>4</sub>
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<sub>3</sub>
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<title xml:lang="en" level="a">Double (n = 2) and triple (n = 3) [M
<sub>4</sub>
Bi
<sub>2n-2</sub>
O
<sub>2n</sub>
]
<sup>x+</sup>
polycationic ribbons in the new Bi
<sub>∼3</sub>
Cd
<sub>∼3.72</sub>
M
<sub>∼1.28</sub>
O
<sub>5</sub>
(PO
<sub>4</sub>
)
<sub>3</sub>
oxyphosphate (M=Co, Cu, Zn)</title>
<author>
<name sortKey="Colmont, Marie" sort="Colmont, Marie" uniqKey="Colmont M" first="Marie" last="Colmont">Marie Colmont</name>
<affiliation wicri:level="3">
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<region type="old region" nuts="2">Nord-Pas-de-Calais</region>
<settlement type="city">Villeneuve d'Ascq</settlement>
</placeName>
</affiliation>
</author>
<author>
<name sortKey="Huve, Marielle" sort="Huve, Marielle" uniqKey="Huve M" first="Marielle" last="Huve">Marielle Huve</name>
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<sZ>1 aut.</sZ>
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<author>
<name sortKey="Ketatni, El Mostafa" sort="Ketatni, El Mostafa" uniqKey="Ketatni E" first="El Mostafa" last="Ketatni">El Mostafa Ketatni</name>
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<s1>Laboratoire d'Electrochmie et Chimie des Matériaux, Faculté des Sciences et Technique Cadi Ayyad, B.P. 523</s1>
<s2>Béni Mellal</s2>
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<sZ>3 aut.</sZ>
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<country>Maroc</country>
<wicri:noRegion>Béni Mellal</wicri:noRegion>
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<name sortKey="Abraham, Francis" sort="Abraham, Francis" uniqKey="Abraham F" first="Francis" last="Abraham">Francis Abraham</name>
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<name sortKey="Mentre, Olivier" sort="Mentre, Olivier" uniqKey="Mentre O" first="Olivier" last="Mentre">Olivier Mentre</name>
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<series>
<title level="j" type="main">Journal of solid state chemistry : (Print)</title>
<title level="j" type="abbreviated">J. solid state chem. : (Print)</title>
<idno type="ISSN">0022-4596</idno>
<imprint>
<date when="2003">2003</date>
</imprint>
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<title level="j" type="main">Journal of solid state chemistry : (Print)</title>
<title level="j" type="abbreviated">J. solid state chem. : (Print)</title>
<idno type="ISSN">0022-4596</idno>
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<keywords scheme="KwdEn" xml:lang="en">
<term>Bismuth oxides</term>
<term>Bismuth phosphates</term>
<term>Cadmium oxides</term>
<term>Cadmium phosphates</term>
<term>Channel structure</term>
<term>Cobalt oxides</term>
<term>Cobalt phosphates</term>
<term>Crystal structure</term>
<term>Electron diffraction</term>
<term>Electron microscopy</term>
<term>Experimental study</term>
<term>Oxyphosphates</term>
<term>Structural models</term>
<term>XRD</term>
</keywords>
<keywords scheme="Pascal" xml:lang="fr">
<term>Etude expérimentale</term>
<term>Diffraction RX</term>
<term>Diffraction électron</term>
<term>Microscopie électronique</term>
<term>Structure cristalline</term>
<term>Bismuth oxyde</term>
<term>Cadmium oxyde</term>
<term>Cobalt oxyde</term>
<term>Bismuth phosphate</term>
<term>Cobalt phosphate</term>
<term>Cadmium phosphate</term>
<term>Structure tunnel</term>
<term>Modèle structure</term>
<term>6166F</term>
<term>Bi3Cd3,72Co1,28O5(PO4)3</term>
<term>Bi Cd Co O P</term>
<term>Oxyphosphate</term>
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<front>
<div type="abstract" xml:lang="en">The crystal structure of the new Bi
<sub>∼3</sub>
Cd
<sub>∼3.72</sub>
Co
<sub>∼1.28</sub>
O
<sub>5</sub>
(PO
<sub>4</sub>
)
<sub>3</sub>
has been refined from single crystal XRD data, R
<sub>1</sub>
= 5.37%, space group Abmm, a = 11.5322(28) Å, b = 5.4760(13) Å, c = 23.2446(56) Å, Z = 4. Compared to Bi
<sub>∼1.2</sub>
M
<sub>∼1.2</sub>
O
<sub>1.5</sub>
(PO
<sub>4</sub>
) and Bi
<sub>∼6.2</sub>
Cu
<sub>∼6.2</sub>
O
<sub>8</sub>
(PO
<sub>4</sub>
)
<sub>5</sub>
, this compound is an additional example of disordered Bi
<sup>3+</sup>
/M
<sup>2+</sup>
oxyphosphate and is well described from the arrangement of double [Bi
<sub>4</sub>
Cd
<sub>4</sub>
O
<sub>6</sub>
]
<sup>8+</sup>
(= D) and triple [Bi
<sub>2</sub>
Cd
<sub>3.44</sub>
Co
<sub>0.56</sub>
O
<sub>4</sub>
]
<sup>6+</sup>
(= T) polycationic ribbons formed of edge-sharing O(Bi,M)
<sub>4</sub>
tetrahedra surrounded by PO
<sub>4</sub>
groups. According to the nomenclature defined in this work, the sequence is TT/DtDt, where t stands for the tunnels created by PO
<sub>4</sub>
between two subsequent double ribbons and occupied by Co
<sup>2+</sup>
. The HREM study allows a clear visualization of the announced sequence by comparison with the refined crystal structure. The Bi
<sup>3+</sup>
/ M
<sup>2+</sup>
statistic disorder at the edges of T and D entities is responsible for the PO
<sub>4</sub>
multi-configuration disorder around a central P atom. Infrared spectroscopy and neutron diffraction of similar compounds (without the highly absorbing Cadmium) even suggests the long range ordering loss for phosphates. Therefore, electron diffraction shows the existence of a modulation vector q* = 1/2a* + (1/3 + ε)b* which pictures cationic ordering in the (001) plane, at the crystallite scale. This ordering is largely lost at the single crystal scale. The existence of mixed Bi
<sup>3+</sup>
/M
<sup>2+</sup>
positions also enables a partial filling of the tunnels by Co
<sup>2+</sup>
and yields a composition range checked by solid state reaction. The title compound can be prepared as a single phase and also the M = Zn
<sup>2+</sup>
term can be obtained in a biphasic mixture. For M = Cu
<sup>2+</sup>
, a monoclinic distortion has been evidenced from XRD and HREM patterns but surprisingly, the orthorhombic ideal form can also be obtained in similar conditions.</div>
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<s1>Double (n = 2) and triple (n = 3) [M
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O
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polycationic ribbons in the new Bi
<sub>∼3</sub>
Cd
<sub>∼3.72</sub>
M
<sub>∼1.28</sub>
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<s0>The crystal structure of the new Bi
<sub>∼3</sub>
Cd
<sub>∼3.72</sub>
Co
<sub>∼1.28</sub>
O
<sub>5</sub>
(PO
<sub>4</sub>
)
<sub>3</sub>
has been refined from single crystal XRD data, R
<sub>1</sub>
= 5.37%, space group Abmm, a = 11.5322(28) Å, b = 5.4760(13) Å, c = 23.2446(56) Å, Z = 4. Compared to Bi
<sub>∼1.2</sub>
M
<sub>∼1.2</sub>
O
<sub>1.5</sub>
(PO
<sub>4</sub>
) and Bi
<sub>∼6.2</sub>
Cu
<sub>∼6.2</sub>
O
<sub>8</sub>
(PO
<sub>4</sub>
)
<sub>5</sub>
, this compound is an additional example of disordered Bi
<sup>3+</sup>
/M
<sup>2+</sup>
oxyphosphate and is well described from the arrangement of double [Bi
<sub>4</sub>
Cd
<sub>4</sub>
O
<sub>6</sub>
]
<sup>8+</sup>
(= D) and triple [Bi
<sub>2</sub>
Cd
<sub>3.44</sub>
Co
<sub>0.56</sub>
O
<sub>4</sub>
]
<sup>6+</sup>
(= T) polycationic ribbons formed of edge-sharing O(Bi,M)
<sub>4</sub>
tetrahedra surrounded by PO
<sub>4</sub>
groups. According to the nomenclature defined in this work, the sequence is TT/DtDt, where t stands for the tunnels created by PO
<sub>4</sub>
between two subsequent double ribbons and occupied by Co
<sup>2+</sup>
. The HREM study allows a clear visualization of the announced sequence by comparison with the refined crystal structure. The Bi
<sup>3+</sup>
/ M
<sup>2+</sup>
statistic disorder at the edges of T and D entities is responsible for the PO
<sub>4</sub>
multi-configuration disorder around a central P atom. Infrared spectroscopy and neutron diffraction of similar compounds (without the highly absorbing Cadmium) even suggests the long range ordering loss for phosphates. Therefore, electron diffraction shows the existence of a modulation vector q* = 1/2a* + (1/3 + ε)b* which pictures cationic ordering in the (001) plane, at the crystallite scale. This ordering is largely lost at the single crystal scale. The existence of mixed Bi
<sup>3+</sup>
/M
<sup>2+</sup>
positions also enables a partial filling of the tunnels by Co
<sup>2+</sup>
and yields a composition range checked by solid state reaction. The title compound can be prepared as a single phase and also the M = Zn
<sup>2+</sup>
term can be obtained in a biphasic mixture. For M = Cu
<sup>2+</sup>
, a monoclinic distortion has been evidenced from XRD and HREM patterns but surprisingly, the orthorhombic ideal form can also be obtained in similar conditions.</s0>
</fC01>
<fC02 i1="01" i2="3">
<s0>001B60A66F4</s0>
</fC02>
<fC03 i1="01" i2="3" l="FRE">
<s0>Etude expérimentale</s0>
<s5>01</s5>
</fC03>
<fC03 i1="01" i2="3" l="ENG">
<s0>Experimental study</s0>
<s5>01</s5>
</fC03>
<fC03 i1="02" i2="3" l="FRE">
<s0>Diffraction RX</s0>
<s5>02</s5>
</fC03>
<fC03 i1="02" i2="3" l="ENG">
<s0>XRD</s0>
<s5>02</s5>
</fC03>
<fC03 i1="03" i2="3" l="FRE">
<s0>Diffraction électron</s0>
<s5>03</s5>
</fC03>
<fC03 i1="03" i2="3" l="ENG">
<s0>Electron diffraction</s0>
<s5>03</s5>
</fC03>
<fC03 i1="04" i2="3" l="FRE">
<s0>Microscopie électronique</s0>
<s5>04</s5>
</fC03>
<fC03 i1="04" i2="3" l="ENG">
<s0>Electron microscopy</s0>
<s5>04</s5>
</fC03>
<fC03 i1="05" i2="3" l="FRE">
<s0>Structure cristalline</s0>
<s5>05</s5>
</fC03>
<fC03 i1="05" i2="3" l="ENG">
<s0>Crystal structure</s0>
<s5>05</s5>
</fC03>
<fC03 i1="06" i2="3" l="FRE">
<s0>Bismuth oxyde</s0>
<s2>NK</s2>
<s5>06</s5>
</fC03>
<fC03 i1="06" i2="3" l="ENG">
<s0>Bismuth oxides</s0>
<s2>NK</s2>
<s5>06</s5>
</fC03>
<fC03 i1="07" i2="3" l="FRE">
<s0>Cadmium oxyde</s0>
<s2>NK</s2>
<s5>07</s5>
</fC03>
<fC03 i1="07" i2="3" l="ENG">
<s0>Cadmium oxides</s0>
<s2>NK</s2>
<s5>07</s5>
</fC03>
<fC03 i1="08" i2="3" l="FRE">
<s0>Cobalt oxyde</s0>
<s2>NK</s2>
<s5>08</s5>
</fC03>
<fC03 i1="08" i2="3" l="ENG">
<s0>Cobalt oxides</s0>
<s2>NK</s2>
<s5>08</s5>
</fC03>
<fC03 i1="09" i2="3" l="FRE">
<s0>Bismuth phosphate</s0>
<s2>NK</s2>
<s5>09</s5>
</fC03>
<fC03 i1="09" i2="3" l="ENG">
<s0>Bismuth phosphates</s0>
<s2>NK</s2>
<s5>09</s5>
</fC03>
<fC03 i1="10" i2="3" l="FRE">
<s0>Cobalt phosphate</s0>
<s2>NK</s2>
<s5>10</s5>
</fC03>
<fC03 i1="10" i2="3" l="ENG">
<s0>Cobalt phosphates</s0>
<s2>NK</s2>
<s5>10</s5>
</fC03>
<fC03 i1="11" i2="3" l="FRE">
<s0>Cadmium phosphate</s0>
<s2>NK</s2>
<s5>11</s5>
</fC03>
<fC03 i1="11" i2="3" l="ENG">
<s0>Cadmium phosphates</s0>
<s2>NK</s2>
<s5>11</s5>
</fC03>
<fC03 i1="12" i2="X" l="FRE">
<s0>Structure tunnel</s0>
<s5>13</s5>
</fC03>
<fC03 i1="12" i2="X" l="ENG">
<s0>Channel structure</s0>
<s5>13</s5>
</fC03>
<fC03 i1="12" i2="X" l="SPA">
<s0>Estructura túnel</s0>
<s5>13</s5>
</fC03>
<fC03 i1="13" i2="3" l="FRE">
<s0>Modèle structure</s0>
<s5>14</s5>
</fC03>
<fC03 i1="13" i2="3" l="ENG">
<s0>Structural models</s0>
<s5>14</s5>
</fC03>
<fC03 i1="14" i2="3" l="FRE">
<s0>6166F</s0>
<s2>PAC</s2>
<s4>INC</s4>
<s5>56</s5>
</fC03>
<fC03 i1="15" i2="3" l="FRE">
<s0>Bi3Cd3,72Co1,28O5(PO4)3</s0>
<s4>INC</s4>
<s5>93</s5>
</fC03>
<fC03 i1="16" i2="3" l="FRE">
<s0>Bi Cd Co O P</s0>
<s4>INC</s4>
<s5>94</s5>
</fC03>
<fC03 i1="17" i2="3" l="FRE">
<s0>Oxyphosphate</s0>
<s4>CD</s4>
<s5>96</s5>
</fC03>
<fC03 i1="17" i2="3" l="ENG">
<s0>Oxyphosphates</s0>
<s4>CD</s4>
<s5>96</s5>
</fC03>
<fC07 i1="01" i2="3" l="FRE">
<s0>Composé minéral</s0>
<s5>81</s5>
</fC07>
<fC07 i1="01" i2="3" l="ENG">
<s0>Inorganic compounds</s0>
<s5>81</s5>
</fC07>
<fC07 i1="02" i2="3" l="FRE">
<s0>Métal transition composé</s0>
<s5>82</s5>
</fC07>
<fC07 i1="02" i2="3" l="ENG">
<s0>Transition element compounds</s0>
<s5>82</s5>
</fC07>
<fN21>
<s1>012</s1>
</fN21>
<fN82>
<s1>PSI</s1>
</fN82>
</pA>
</standard>
</inist>
<affiliations>
<list>
<country>
<li>France</li>
<li>Maroc</li>
</country>
<region>
<li>Hauts-de-France</li>
<li>Nord-Pas-de-Calais</li>
</region>
<settlement>
<li>Villeneuve d'Ascq</li>
</settlement>
</list>
<tree>
<country name="France">
<region name="Hauts-de-France">
<name sortKey="Colmont, Marie" sort="Colmont, Marie" uniqKey="Colmont M" first="Marie" last="Colmont">Marie Colmont</name>
</region>
<name sortKey="Abraham, Francis" sort="Abraham, Francis" uniqKey="Abraham F" first="Francis" last="Abraham">Francis Abraham</name>
<name sortKey="Huve, Marielle" sort="Huve, Marielle" uniqKey="Huve M" first="Marielle" last="Huve">Marielle Huve</name>
<name sortKey="Mentre, Olivier" sort="Mentre, Olivier" uniqKey="Mentre O" first="Olivier" last="Mentre">Olivier Mentre</name>
</country>
<country name="Maroc">
<noRegion>
<name sortKey="Ketatni, El Mostafa" sort="Ketatni, El Mostafa" uniqKey="Ketatni E" first="El Mostafa" last="Ketatni">El Mostafa Ketatni</name>
</noRegion>
</country>
</tree>
</affiliations>
</record>

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   |wiki=    Wicri/Terre
   |area=    CobaltMaghrebV1
   |flux=    PascalFrancis
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   |clé=     Pascal:04-0016354
   |texte=   Double (n = 2) and triple (n = 3) [M4Bi2n-2O2n]x+ polycationic ribbons in the new Bi∼3Cd∼3.72M∼1.28O5(PO4)3 oxyphosphate (M=Co, Cu, Zn)
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Data generation: Tue Nov 14 12:56:51 2017. Site generation: Mon Feb 12 07:59:49 2024