Synthesis, Nuclear, and Magnetic Structures and Magnetic Properties of [Mn3(OH)2(SO4)2(H2O)2]
Identifieur interne : 001048 ( Istex/Corpus ); précédent : 001047; suivant : 001049Synthesis, Nuclear, and Magnetic Structures and Magnetic Properties of [Mn3(OH)2(SO4)2(H2O)2]
Auteurs : Mohsen Ben Salah ; Serge Vilminot ; Gilles André ; Mireille Richard-Plouet ; Françoise Bourée-Vigneron ; Tahar Mhiri ; Mohamedally KurmooSource :
- Chemistry – A European Journal [ 0947-6539 ] ; 2004-04-19.
English descriptors
Abstract
[Mn3(OH)2(SO4)2(H2O)2] and its deuterated anlaogue were synthesized by a hydrothermal technique and characterized by differential thermal analysis, thermogravimetric analysis, and IR spectroscopy. Its nuclear structure, determined by single‐crystal X‐ray analysis and Rietveld analysis of neutron powder‐diffraction data, consists of a 3D network of chains of edge‐sharing Mn(1)O6, running along the c axis, connected by the apices of Mn(2)O6 and SO4 units. It is isostructural to the nickel analogue. Determination of the magnetic structure and measurements of magnetization and heat capacity indicate the coexistence of both magnetic long‐range ordering (LRO) and short‐range ordering (SRO) below a Néel temperature of 26 K, while the SRO is retained at higher temperatures. The moments of the two independent Mn atoms lie in the bc plane, and that of Mn(1) rotates continuously by 54° towards the c axis on decreasing the temperature from 25 to 1.4 K. While the SRO may be associated with frustration of the moments within a Mn3 trimer, the LRO is achieved by antiparallel alignment of the four symmetry‐related trimers within the magnetic unit cell. A spin‐flop field, measured by dc and ac magnetization on a SQUID, is observed at 15 kOe.
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DOI: 10.1002/chem.200305645
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Strasbourg Cedex 2, France</mods:affiliation></affiliation><affiliation><mods:affiliation>Laboratoire de L'Etat Solide, Faculté des Sciences, 3038 Sfax, Tunisia</mods:affiliation></affiliation></author><author><name sortKey="Vilminot, Serge" sort="Vilminot, Serge" uniqKey="Vilminot S" first="Serge" last="Vilminot">Serge Vilminot</name><affiliation><mods:affiliation>Groupe des Matériaux Inorganiques, IPCMS, UMR 7504 CNRS‐ULP, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France</mods:affiliation></affiliation><affiliation><mods:affiliation>E-mail: vilminot@ipcms.u‐strasbg.fr</mods:affiliation></affiliation></author><author><name sortKey="Andre, Gilles" sort="Andre, Gilles" uniqKey="Andre G" first="Gilles" last="André">Gilles André</name><affiliation><mods:affiliation>Laboratoire Léon Brillouin, CEA‐CNRS, CEA Saclay, 91191 Gif‐sur‐Yvette Cedex, France</mods:affiliation></affiliation></author><author><name sortKey="Richard Louet, Mireille" sort="Richard Louet, Mireille" uniqKey="Richard Louet M" first="Mireille" last="Richard-Plouet">Mireille Richard-Plouet</name><affiliation><mods:affiliation>Groupe des Matériaux Inorganiques, IPCMS, UMR 7504 CNRS‐ULP, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France</mods:affiliation></affiliation><affiliation><mods:affiliation>Institut des Matériaux Jean Rouxel, UMR CNRS 6502, Laboratoire de Chimie des Solides, 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 03, France</mods:affiliation></affiliation></author><author><name sortKey="Bouree Igneron, Francoise" sort="Bouree Igneron, Francoise" uniqKey="Bouree Igneron F" first="Françoise" last="Bourée-Vigneron">Françoise Bourée-Vigneron</name><affiliation><mods:affiliation>Laboratoire Léon Brillouin, CEA‐CNRS, CEA Saclay, 91191 Gif‐sur‐Yvette Cedex, France</mods:affiliation></affiliation></author><author><name sortKey="Mhiri, Tahar" sort="Mhiri, Tahar" uniqKey="Mhiri T" first="Tahar" last="Mhiri">Tahar Mhiri</name><affiliation><mods:affiliation>Laboratoire de L'Etat Solide, Faculté des Sciences, 3038 Sfax, Tunisia</mods:affiliation></affiliation></author><author><name sortKey="Kurmoo, Mohamedally" sort="Kurmoo, Mohamedally" uniqKey="Kurmoo M" first="Mohamedally" last="Kurmoo">Mohamedally Kurmoo</name><affiliation><mods:affiliation>Groupe des Matériaux Inorganiques, IPCMS, UMR 7504 CNRS‐ULP, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France</mods:affiliation></affiliation></author></analytic><monogr></monogr><series><title level="j">Chemistry – A European Journal</title><title level="j" type="abbrev">Chemistry – A European Journal</title><idno type="ISSN">0947-6539</idno><idno type="eISSN">1521-3765</idno><imprint><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2004-04-19">2004-04-19</date><biblScope unit="volume">10</biblScope><biblScope unit="issue">8</biblScope><biblScope unit="page" from="2048">2048</biblScope><biblScope unit="page" to="2057">2057</biblScope></imprint><idno type="ISSN">0947-6539</idno></series><idno type="istex">EC88300ECDF9D384AE6091F55E31582693F09D9A</idno><idno type="DOI">10.1002/chem.200305645</idno><idno type="ArticleID">CHEM200305645</idno></biblStruct></sourceDesc><seriesStmt><idno type="ISSN">0947-6539</idno></seriesStmt></fileDesc><profileDesc><textClass><keywords scheme="KwdEn" xml:lang="en"><term>hydrothermal synthesis</term><term>hydroxide sulfates</term><term>magnetic properties</term><term>manganese</term></keywords></textClass><langUsage><language ident="en">en</language></langUsage></profileDesc></teiHeader><front><div type="abstract" xml:lang="en">[Mn3(OH)2(SO4)2(H2O)2] and its deuterated anlaogue were synthesized by a hydrothermal technique and characterized by differential thermal analysis, thermogravimetric analysis, and IR spectroscopy. Its nuclear structure, determined by single‐crystal X‐ray analysis and Rietveld analysis of neutron powder‐diffraction data, consists of a 3D network of chains of edge‐sharing Mn(1)O6, running along the c axis, connected by the apices of Mn(2)O6 and SO4 units. It is isostructural to the nickel analogue. Determination of the magnetic structure and measurements of magnetization and heat capacity indicate the coexistence of both magnetic long‐range ordering (LRO) and short‐range ordering (SRO) below a Néel temperature of 26 K, while the SRO is retained at higher temperatures. The moments of the two independent Mn atoms lie in the bc plane, and that of Mn(1) rotates continuously by 54° towards the c axis on decreasing the temperature from 25 to 1.4 K. While the SRO may be associated with frustration of the moments within a Mn3 trimer, the LRO is achieved by antiparallel alignment of the four symmetry‐related trimers within the magnetic unit cell. A spin‐flop field, measured by dc and ac magnetization on a SQUID, is observed at 15 kOe.</div></front></TEI><istex><corpusName>wiley</corpusName><author><json:item><name>Mohsen Ben Salah Dr.</name><affiliations><json:string>Groupe des Matériaux Inorganiques, IPCMS, UMR 7504 CNRS‐ULP, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France</json:string><json:string>Laboratoire de L'Etat Solide, Faculté des Sciences, 3038 Sfax, Tunisia</json:string></affiliations></json:item><json:item><name>Serge Vilminot Dr.</name><affiliations><json:string>Groupe des Matériaux Inorganiques, IPCMS, UMR 7504 CNRS‐ULP, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France</json:string><json:string>E-mail: vilminot@ipcms.u‐strasbg.fr</json:string></affiliations></json:item><json:item><name>Gilles André Dr.</name><affiliations><json:string>Laboratoire Léon Brillouin, CEA‐CNRS, CEA Saclay, 91191 Gif‐sur‐Yvette Cedex, France</json:string></affiliations></json:item><json:item><name>Mireille Richard‐Plouet Dr.</name><affiliations><json:string>Groupe des Matériaux Inorganiques, IPCMS, UMR 7504 CNRS‐ULP, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France</json:string><json:string>Institut des Matériaux Jean Rouxel, UMR CNRS 6502, Laboratoire de Chimie des Solides, 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 03, France</json:string></affiliations></json:item><json:item><name>Françoise Bourée‐Vigneron Dr.</name><affiliations><json:string>Laboratoire Léon Brillouin, CEA‐CNRS, CEA Saclay, 91191 Gif‐sur‐Yvette Cedex, France</json:string></affiliations></json:item><json:item><name>Tahar Mhiri Prof. Dr.</name><affiliations><json:string>Laboratoire de L'Etat Solide, Faculté des Sciences, 3038 Sfax, Tunisia</json:string></affiliations></json:item><json:item><name>Mohamedally Kurmoo Dr.</name><affiliations><json:string>Groupe des Matériaux Inorganiques, IPCMS, UMR 7504 CNRS‐ULP, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France</json:string></affiliations></json:item></author><subject><json:item><lang><json:string>eng</json:string></lang><value>hydrothermal synthesis</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>hydroxide sulfates</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>magnetic properties</value></json:item><json:item><lang><json:string>eng</json:string></lang><value>manganese</value></json:item></subject><articleId><json:string>CHEM200305645</json:string></articleId><language><json:string>eng</json:string></language><originalGenre><json:string>article</json:string></originalGenre><abstract>[Mn3(OH)2(SO4)2(H2O)2] and its deuterated anlaogue were synthesized by a hydrothermal technique and characterized by differential thermal analysis, thermogravimetric analysis, and IR spectroscopy. Its nuclear structure, determined by single‐crystal X‐ray analysis and Rietveld analysis of neutron powder‐diffraction data, consists of a 3D network of chains of edge‐sharing Mn(1)O6, running along the c axis, connected by the apices of Mn(2)O6 and SO4 units. It is isostructural to the nickel analogue. Determination of the magnetic structure and measurements of magnetization and heat capacity indicate the coexistence of both magnetic long‐range ordering (LRO) and short‐range ordering (SRO) below a Néel temperature of 26 K, while the SRO is retained at higher temperatures. The moments of the two independent Mn atoms lie in the bc plane, and that of Mn(1) rotates continuously by 54° towards the c axis on decreasing the temperature from 25 to 1.4 K. While the SRO may be associated with frustration of the moments within a Mn3 trimer, the LRO is achieved by antiparallel alignment of the four symmetry‐related trimers within the magnetic unit cell. A spin‐flop field, measured by dc and ac magnetization on a SQUID, is observed at 15 kOe.</abstract><qualityIndicators><score>7.292</score><pdfVersion>1.2</pdfVersion><pdfPageSize>595 x 842 pts (A4)</pdfPageSize><refBibsNative>true</refBibsNative><keywordCount>4</keywordCount><abstractCharCount>1243</abstractCharCount><pdfWordCount>7724</pdfWordCount><pdfCharCount>45615</pdfCharCount><pdfPageCount>10</pdfPageCount><abstractWordCount>191</abstractWordCount></qualityIndicators><title>Synthesis, Nuclear, and Magnetic Structures and Magnetic Properties of [Mn3(OH)2(SO4)2(H2O)2]</title><genre><json:string>article</json:string></genre><host><volume>10</volume><publisherId><json:string>CHEM</json:string></publisherId><pages><total>10</total><last>2057</last><first>2048</first></pages><issn><json:string>0947-6539</json:string></issn><issue>8</issue><subject><json:item><value>Full Paper</value></json:item></subject><genre><json:string>journal</json:string></genre><language><json:string>unknown</json:string></language><eissn><json:string>1521-3765</json:string></eissn><title>Chemistry – A European Journal</title><doi><json:string>10.1002/(ISSN)1521-3765</json:string></doi></host><publicationDate>2004</publicationDate><copyrightDate>2004</copyrightDate><doi><json:string>10.1002/chem.200305645</json:string></doi><id>EC88300ECDF9D384AE6091F55E31582693F09D9A</id><score>0.049087018</score><fulltext><json:item><original>true</original><mimetype>application/pdf</mimetype><extension>pdf</extension><uri>https://api.istex.fr/document/EC88300ECDF9D384AE6091F55E31582693F09D9A/fulltext/pdf</uri></json:item><json:item><original>false</original><mimetype>application/zip</mimetype><extension>zip</extension><uri>https://api.istex.fr/document/EC88300ECDF9D384AE6091F55E31582693F09D9A/fulltext/zip</uri></json:item><istex:fulltextTEI uri="https://api.istex.fr/document/EC88300ECDF9D384AE6091F55E31582693F09D9A/fulltext/tei"><teiHeader><fileDesc><titleStmt><title level="a" type="main" xml:lang="en">Synthesis, Nuclear, and Magnetic Structures and Magnetic Properties of [Mn3(OH)2(SO4)2(H2O)2]</title></titleStmt><publicationStmt><authority>ISTEX</authority><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><availability><p>Copyright © 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</p></availability><date>2004</date></publicationStmt><sourceDesc><biblStruct type="inbook"><analytic><title level="a" type="main" xml:lang="en">Synthesis, Nuclear, and Magnetic Structures and Magnetic Properties of [Mn3(OH)2(SO4)2(H2O)2]</title><author xml:id="author-1"><persName><forename type="first">Mohsen</forename><surname>Ben Salah</surname></persName><roleName type="degree">Dr.</roleName><affiliation>Groupe des Matériaux Inorganiques, IPCMS, UMR 7504 CNRS‐ULP, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France</affiliation><affiliation>Laboratoire de L'Etat Solide, Faculté des Sciences, 3038 Sfax, Tunisia</affiliation></author><author xml:id="author-2"><persName><forename type="first">Serge</forename><surname>Vilminot</surname></persName><roleName type="degree">Dr.</roleName><email>vilminot@ipcms.u‐strasbg.fr</email><affiliation>Groupe des Matériaux Inorganiques, IPCMS, UMR 7504 CNRS‐ULP, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France</affiliation></author><author xml:id="author-3"><persName><forename type="first">Gilles</forename><surname>André</surname></persName><roleName type="degree">Dr.</roleName><affiliation>Laboratoire Léon Brillouin, CEA‐CNRS, CEA Saclay, 91191 Gif‐sur‐Yvette Cedex, France</affiliation></author><author xml:id="author-4"><persName><forename type="first">Mireille</forename><surname>Richard‐Plouet</surname></persName><roleName type="degree">Dr.</roleName><affiliation>Groupe des Matériaux Inorganiques, IPCMS, UMR 7504 CNRS‐ULP, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France</affiliation><affiliation>Institut des Matériaux Jean Rouxel, UMR CNRS 6502, Laboratoire de Chimie des Solides, 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 03, France</affiliation></author><author xml:id="author-5"><persName><forename type="first">Françoise</forename><surname>Bourée‐Vigneron</surname></persName><roleName type="degree">Dr.</roleName><affiliation>Laboratoire Léon Brillouin, CEA‐CNRS, CEA Saclay, 91191 Gif‐sur‐Yvette Cedex, France</affiliation></author><author xml:id="author-6"><persName><forename type="first">Tahar</forename><surname>Mhiri</surname></persName><roleName type="degree">Prof. Dr.</roleName><affiliation>Laboratoire de L'Etat Solide, Faculté des Sciences, 3038 Sfax, Tunisia</affiliation></author><author xml:id="author-7"><persName><forename type="first">Mohamedally</forename><surname>Kurmoo</surname></persName><roleName type="degree">Dr.</roleName><affiliation>Groupe des Matériaux Inorganiques, IPCMS, UMR 7504 CNRS‐ULP, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France</affiliation></author></analytic><monogr><title level="j">Chemistry – A European Journal</title><title level="j" type="abbrev">Chemistry – A European Journal</title><idno type="pISSN">0947-6539</idno><idno type="eISSN">1521-3765</idno><idno type="DOI">10.1002/(ISSN)1521-3765</idno><imprint><publisher>WILEY‐VCH Verlag</publisher><pubPlace>Weinheim</pubPlace><date type="published" when="2004-04-19"></date><biblScope unit="volume">10</biblScope><biblScope unit="issue">8</biblScope><biblScope unit="page" from="2048">2048</biblScope><biblScope unit="page" to="2057">2057</biblScope></imprint></monogr><idno type="istex">EC88300ECDF9D384AE6091F55E31582693F09D9A</idno><idno type="DOI">10.1002/chem.200305645</idno><idno type="ArticleID">CHEM200305645</idno></biblStruct></sourceDesc></fileDesc><profileDesc><creation><date>2004</date></creation><langUsage><language ident="en">en</language></langUsage><abstract xml:lang="en"><p>[Mn3(OH)2(SO4)2(H2O)2] and its deuterated anlaogue were synthesized by a hydrothermal technique and characterized by differential thermal analysis, thermogravimetric analysis, and IR spectroscopy. Its nuclear structure, determined by single‐crystal X‐ray analysis and Rietveld analysis of neutron powder‐diffraction data, consists of a 3D network of chains of edge‐sharing Mn(1)O6, running along the c axis, connected by the apices of Mn(2)O6 and SO4 units. It is isostructural to the nickel analogue. Determination of the magnetic structure and measurements of magnetization and heat capacity indicate the coexistence of both magnetic long‐range ordering (LRO) and short‐range ordering (SRO) below a Néel temperature of 26 K, while the SRO is retained at higher temperatures. The moments of the two independent Mn atoms lie in the bc plane, and that of Mn(1) rotates continuously by 54° towards the c axis on decreasing the temperature from 25 to 1.4 K. While the SRO may be associated with frustration of the moments within a Mn3 trimer, the LRO is achieved by antiparallel alignment of the four symmetry‐related trimers within the magnetic unit cell. A spin‐flop field, measured by dc and ac magnetization on a SQUID, is observed at 15 kOe.</p></abstract><abstract xml:lang="fr"><p>[Mn3(OH)2(SO4)2(H2O)2] et son équivalent deutérié ont été préparés par synthèse hydrothermale et caractérisés par ATG‐ATD et spectroscopie infrarouge. Sa structure, affinée à partir de données de diffraction RX sur monocristal, est analogue à celle du sel de nickel correspondant et fait apparaître un réseau 3D formé par des chaînes d′octaèdres Mn(1)O6 liés par une arête, chaînes connectées entre elles par un sommet commun à des octaèdres Mn(2)O6 et des tétraèdres SO4. La détermination de la structure magnétique et les mesures des propriétés magnétiques et de chaleur spécifique indiquent la coexistence d′un ordre magnétique à longue distance (LRO) et à courte distance (SRO) en‐dessous de la température de Néel TN de 26 K, l′ordre à courte distance s′établissant à plus haute température. Les moments magnétiques des deux atomes Mn indépendants se trouvent dans le plan bc. Alors que celui de Mn(2) est toujours dirigé selon l′axe c, celui de Mn(1) se rapproche progressivement de cette direction lorsque la température est abaissée de TN à 1,4 K, la rotation globale étant de 54°. Alors que l′ordre à courte distance peut être dû à la frustation des moments à l′intérieur des trimères Mn3, en interaction antiferromagnétique, l′ordre à longue distance résulte de l′alignement antiparallèle des quatre trimères de la maille magnétique. Un champ de spin‐flop, mesuré par aimantation dc et ac, est observé à 15 kOe.</p></abstract><abstract><p>Both long‐ and short‐range magnetic ordering below its Néel temperature of 26 K are exhibited by [Mn3(OH)2(SO4)2(H2O)2], which was obtained by hydrothermal synthesis and characterized by X‐ray and neutron diffraction. The crystal structure consists of a three‐dimensional arrangement of MnO6, μ3‐OH, and μ4‐SO4 units. In the magnetic structure (see picture), the moments lie in the bc plane, and the moment of Mn(1) rotates from 74 to 20° with respect to the c axis on cooling from 26 to 1.4 K, while that of Mn(2) remains along the c axis.</p></abstract><textClass xml:lang="en"><keywords scheme="keyword"><list><head>keywords</head><item><term>hydrothermal synthesis</term></item><item><term>hydroxide sulfates</term></item><item><term>magnetic properties</term></item><item><term>manganese</term></item></list></keywords></textClass><textClass><keywords scheme="Journal Subject"><list><head>article-category</head><item><term>Full Paper</term></item></list></keywords></textClass></profileDesc><revisionDesc><change when="2003-10-21">Received</change><change when="2004-04-19">Published</change></revisionDesc></teiHeader></istex:fulltextTEI><json:item><original>false</original><mimetype>text/plain</mimetype><extension>txt</extension><uri>https://api.istex.fr/document/EC88300ECDF9D384AE6091F55E31582693F09D9A/fulltext/txt</uri></json:item></fulltext><metadata><istex:metadataXml wicri:clean="Wiley, elements deleted: body"><istex:xmlDeclaration>version="1.0" encoding="UTF-8" standalone="yes"</istex:xmlDeclaration><istex:document><component version="2.0" type="serialArticle" xml:lang="en"><header><publicationMeta level="product"><publisherInfo><publisherName>WILEY‐VCH Verlag</publisherName><publisherLoc>Weinheim</publisherLoc></publisherInfo><doi registered="yes">10.1002/(ISSN)1521-3765</doi><issn type="print">0947-6539</issn><issn type="electronic">1521-3765</issn><idGroup><id type="product" value="CHEM"></id></idGroup><titleGroup><title type="main" xml:lang="en">Chemistry – A European Journal</title><title type="short">Chemistry – A European Journal</title></titleGroup></publicationMeta><publicationMeta level="part" position="80"><doi origin="wiley" registered="yes">10.1002/chem.v10:8</doi><numberingGroup><numbering type="journalVolume" number="10">10</numbering><numbering type="journalIssue">8</numbering></numberingGroup><coverDate startDate="2004-04-19">April 19, 2004</coverDate></publicationMeta><publicationMeta level="unit" type="article" position="23" status="forIssue"><doi origin="wiley" registered="yes">10.1002/chem.200305645</doi><idGroup><id type="unit" value="CHEM200305645"></id></idGroup><countGroup><count type="pageTotal" number="10"></count></countGroup><titleGroup><title type="articleCategory">Full Paper</title></titleGroup><copyright ownership="publisher">Copyright © 2004 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim</copyright><eventGroup><event type="manuscriptReceived" date="2003-10-21"></event><event type="manuscriptRevised" date="2003-12-19"></event><event type="firstOnline" date="2004-04-07"></event><event type="publishedOnlineFinalForm" date="2004-04-07"></event><event type="xmlConverted" agent="Converter:JWSART34_TO_WML3G version:2.3.1 mode:FullText source:FullText result:FullText mathml2tex" date="2010-02-20"></event><event type="xmlConverted" agent="Converter:WILEY_ML3G_TO_WILEY_ML3GV2 version:3.8.8" date="2014-01-09"></event><event type="xmlConverted" agent="Converter:WML3G_To_WML3G version:4.1.7 mode:FullText,remove_FC" date="2014-10-15"></event></eventGroup><numberingGroup><numbering type="pageFirst">2048</numbering><numbering type="pageLast">2057</numbering></numberingGroup><linkGroup><link type="toTypesetVersion" href="file:CHEM.CHEM200305645.pdf"></link></linkGroup></publicationMeta><contentMeta><countGroup><count type="figureTotal" number="11"></count><count type="tableTotal" number="7"></count><count type="referenceTotal" number="61"></count></countGroup><titleGroup><title type="main" xml:lang="en">Synthesis, Nuclear, and Magnetic Structures and Magnetic Properties of [Mn<sub>3</sub>(OH)<sub>2</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>]</title></titleGroup><creators><creator xml:id="au1" creatorRole="author" affiliationRef="#aa #ab"><personName><givenNames>Mohsen</givenNames><familyName>Ben Salah</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au2" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Serge</givenNames><familyName>Vilminot</familyName><degrees>Dr.</degrees></personName><contactDetails><email normalForm="vilminot@ipcms.u-strasbg.fr">vilminot@ipcms.u‐strasbg.fr</email></contactDetails></creator><creator xml:id="au3" creatorRole="author" affiliationRef="#ac"><personName><givenNames>Gilles</givenNames><familyName>André</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au4" creatorRole="author" affiliationRef="#aa #ad"><personName><givenNames>Mireille</givenNames><familyName>Richard‐Plouet</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au5" creatorRole="author" affiliationRef="#ac"><personName><givenNames>Françoise</givenNames><familyName>Bourée‐Vigneron</familyName><degrees>Dr.</degrees></personName></creator><creator xml:id="au6" creatorRole="author" affiliationRef="#ab"><personName><givenNames>Tahar</givenNames><familyName>Mhiri</familyName><degrees>Prof. Dr.</degrees></personName></creator><creator xml:id="au7" creatorRole="author" affiliationRef="#aa"><personName><givenNames>Mohamedally</givenNames><familyName>Kurmoo</familyName><degrees>Dr.</degrees></personName></creator></creators><affiliationGroup><affiliation xml:id="aa" countryCode="FR" type="organization"><unparsedAffiliation>Groupe des Matériaux Inorganiques, IPCMS, UMR 7504 CNRS‐ULP, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France</unparsedAffiliation></affiliation><affiliation xml:id="ab" countryCode="TN" type="organization"><unparsedAffiliation>Laboratoire de L'Etat Solide, Faculté des Sciences, 3038 Sfax, Tunisia</unparsedAffiliation></affiliation><affiliation xml:id="ac" countryCode="FR" type="organization"><unparsedAffiliation>Laboratoire Léon Brillouin, CEA‐CNRS, CEA Saclay, 91191 Gif‐sur‐Yvette Cedex, France</unparsedAffiliation></affiliation><affiliation xml:id="ad" countryCode="FR" type="organization"><unparsedAffiliation>Institut des Matériaux Jean Rouxel, UMR CNRS 6502, Laboratoire de Chimie des Solides, 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 03, France</unparsedAffiliation></affiliation></affiliationGroup><keywordGroup xml:lang="en" type="author"><keyword xml:id="kwd1">hydrothermal synthesis</keyword><keyword xml:id="kwd2">hydroxide sulfates</keyword><keyword xml:id="kwd3">magnetic properties</keyword><keyword xml:id="kwd4">manganese</keyword></keywordGroup><supportingInformation><p>Supporting information for this article is available on the WWW under <url href="http://www.wiley-vch.de/contents/jc_2111/2004/f5645_s.pdf">http://www.wiley‐vch.de/contents/jc_2111/2004/f5645_s.pdf</url> or from the author.</p></supportingInformation><abstractGroup><abstract type="main" xml:lang="en"><title type="main">Abstract</title><p>[Mn<sub>3</sub>(OH)<sub>2</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>] and its deuterated anlaogue were synthesized by a hydrothermal technique and characterized by differential thermal analysis, thermogravimetric analysis, and IR spectroscopy. Its nuclear structure, determined by single‐crystal X‐ray analysis and Rietveld analysis of neutron powder‐diffraction data, consists of a 3D network of chains of edge‐sharing Mn(1)O<sub>6</sub>, running along the <i>c</i> axis, connected by the apices of Mn(2)O<sub>6</sub> and SO<sub>4</sub> units. It is isostructural to the nickel analogue. Determination of the magnetic structure and measurements of magnetization and heat capacity indicate the coexistence of both magnetic long‐range ordering (LRO) and short‐range ordering (SRO) below a Néel temperature of 26 K, while the SRO is retained at higher temperatures. The moments of the two independent Mn atoms lie in the <i>bc</i> plane, and that of Mn(1) rotates continuously by 54° towards the <i>c</i> axis on decreasing the temperature from 25 to 1.4 K. While the SRO may be associated with frustration of the moments within a Mn<sub>3</sub> trimer, the LRO is achieved by antiparallel alignment of the four symmetry‐related trimers within the magnetic unit cell. A spin‐flop field, measured by dc and ac magnetization on a SQUID, is observed at 15 kOe.</p></abstract><abstract type="main" xml:lang="fr"><p><i>[Mn</i><sub><i>3</i></sub><i>(OH)</i><sub><i>2</i></sub><i>(SO</i><sub><i>4</i></sub><i>)</i><sub><i>2</i></sub><i>(H</i><sub><i>2</i></sub><i>O)</i><sub><i>2</i></sub><i>] et son équivalent deutérié ont été préparés par synthèse hydrothermale et caractérisés par ATG‐ATD et spectroscopie infrarouge</i>. <i>Sa structure</i>, <i>affinée à partir de données de diffraction RX sur monocristal</i>, <i>est analogue à celle du sel de nickel correspondant et fait apparaître un réseau 3D formé par des chaînes d′octaèdres Mn(1)O</i><sub><i>6</i></sub> <i>liés par une arête</i>, <i>chaînes connectées entre elles par un sommet commun à des octaèdres Mn(2)O</i><sub><i>6</i></sub> <i>et des tétraèdres SO</i><sub><i>4</i></sub>. <i>La détermination de la structure magnétique et les mesures des propriétés magnétiques et de chaleur spécifique indiquent la coexistence d′un ordre magnétique à longue distance (LRO) et à courte distance (SRO) en‐dessous de la température de Néel</i> T<sub><i>N</i></sub> <i>de 26 K</i>, <i>l′ordre à courte distance s′établissant à plus haute température</i>. <i>Les moments magnétiques des deux atomes Mn indépendants se trouvent dans le plan bc</i>. <i>Alors que celui de Mn(2) est toujours dirigé selon l′axe c</i>, <i>celui de Mn(1) se rapproche progressivement de cette direction lorsque la température est abaissée de</i> T<sub><i>N</i></sub> <i>à 1</i>,<i>4 K</i>, <i>la rotation globale étant de 54°</i>. <i>Alors que l′ordre à courte distance peut être dû à la frustation des moments à l′intérieur des trimères Mn</i><sub><i>3</i></sub>, <i>en interaction antiferromagnétique</i>, <i>l′ordre à longue distance résulte de l′alignement antiparallèle des quatre trimères de la maille magnétique</i>. <i>Un champ de spin‐flop</i>, <i>mesuré par aimantation dc et ac</i>, <i>est observé à 15 kOe</i>.</p></abstract><abstract type="graphical" xml:lang="en"><p><b>Both long‐ and short‐range magnetic ordering</b> below its Néel temperature of 26 K are exhibited by [Mn<sub>3</sub>(OH)<sub>2</sub>(SO<sub>4</sub>)<sub>2</sub>(H<sub>2</sub>O)<sub>2</sub>], which was obtained by hydrothermal synthesis and characterized by X‐ray and neutron diffraction. The crystal structure consists of a three‐dimensional arrangement of MnO<sub>6</sub>, μ<sub>3</sub>‐OH, and μ<sub>4</sub>‐SO<sub>4</sub> units. In the magnetic structure (see picture), the moments lie in the <i>bc</i> plane, and the moment of Mn(1) rotates from 74 to 20° with respect to the <i>c</i> axis on cooling from 26 to 1.4 K, while that of Mn(2) remains along the <i>c</i> axis.<blockFixed type="graphic"><mediaResourceGroup><mediaResource alt="image" eRights="yes" copyright="WILEY-VCH" href="urn:x-wiley:09476539:media:CHEM200305645:content"></mediaResource><mediaResource alt="thumbnail image" rendition="webLoRes" mimeType="image/gif" href=""></mediaResource><mediaResource alt="original image" rendition="webOriginal" mimeType="image/gif" href=""></mediaResource><mediaResource alt="magnified image" rendition="webHiRes" mimeType="image/gif" href=""></mediaResource></mediaResourceGroup></blockFixed></p></abstract></abstractGroup></contentMeta></header></component></istex:document></istex:metadataXml><mods version="3.6"><titleInfo lang="en"><title>Synthesis, Nuclear, and Magnetic Structures and Magnetic Properties of [Mn3(OH)2(SO4)2(H2O)2]</title></titleInfo><titleInfo type="alternative" contentType="CDATA" lang="en"><title>Synthesis, Nuclear, and Magnetic Structures and Magnetic Properties of [Mn3(OH)2(SO4)2(H2O)2]</title></titleInfo><name type="personal"><namePart type="given">Mohsen</namePart><namePart type="family">Ben Salah</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Groupe des Matériaux Inorganiques, IPCMS, UMR 7504 CNRS‐ULP, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France</affiliation><affiliation>Laboratoire de L'Etat Solide, Faculté des Sciences, 3038 Sfax, Tunisia</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Serge</namePart><namePart type="family">Vilminot</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Groupe des Matériaux Inorganiques, IPCMS, UMR 7504 CNRS‐ULP, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France</affiliation><affiliation>E-mail: vilminot@ipcms.u‐strasbg.fr</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Gilles</namePart><namePart type="family">André</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Laboratoire Léon Brillouin, CEA‐CNRS, CEA Saclay, 91191 Gif‐sur‐Yvette Cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Mireille</namePart><namePart type="family">Richard‐Plouet</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Groupe des Matériaux Inorganiques, IPCMS, UMR 7504 CNRS‐ULP, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France</affiliation><affiliation>Institut des Matériaux Jean Rouxel, UMR CNRS 6502, Laboratoire de Chimie des Solides, 2 rue de la Houssinière, BP 32229, 44322 Nantes Cedex 03, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Françoise</namePart><namePart type="family">Bourée‐Vigneron</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Laboratoire Léon Brillouin, CEA‐CNRS, CEA Saclay, 91191 Gif‐sur‐Yvette Cedex, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Tahar</namePart><namePart type="family">Mhiri</namePart><namePart type="termsOfAddress">Prof. Dr.</namePart><affiliation>Laboratoire de L'Etat Solide, Faculté des Sciences, 3038 Sfax, Tunisia</affiliation><role><roleTerm type="text">author</roleTerm></role></name><name type="personal"><namePart type="given">Mohamedally</namePart><namePart type="family">Kurmoo</namePart><namePart type="termsOfAddress">Dr.</namePart><affiliation>Groupe des Matériaux Inorganiques, IPCMS, UMR 7504 CNRS‐ULP, 23 rue du Loess, BP 43, 67034 Strasbourg Cedex 2, France</affiliation><role><roleTerm type="text">author</roleTerm></role></name><typeOfResource>text</typeOfResource><genre type="article" displayLabel="article"></genre><originInfo><publisher>WILEY‐VCH Verlag</publisher><place><placeTerm type="text">Weinheim</placeTerm></place><dateIssued encoding="w3cdtf">2004-04-19</dateIssued><dateCaptured encoding="w3cdtf">2003-10-21</dateCaptured><copyrightDate encoding="w3cdtf">2004</copyrightDate></originInfo><language><languageTerm type="code" authority="rfc3066">en</languageTerm><languageTerm type="code" authority="iso639-2b">eng</languageTerm></language><physicalDescription><internetMediaType>text/html</internetMediaType><extent unit="figures">11</extent><extent unit="tables">7</extent><extent unit="references">61</extent></physicalDescription><abstract lang="en">[Mn3(OH)2(SO4)2(H2O)2] and its deuterated anlaogue were synthesized by a hydrothermal technique and characterized by differential thermal analysis, thermogravimetric analysis, and IR spectroscopy. Its nuclear structure, determined by single‐crystal X‐ray analysis and Rietveld analysis of neutron powder‐diffraction data, consists of a 3D network of chains of edge‐sharing Mn(1)O6, running along the c axis, connected by the apices of Mn(2)O6 and SO4 units. It is isostructural to the nickel analogue. Determination of the magnetic structure and measurements of magnetization and heat capacity indicate the coexistence of both magnetic long‐range ordering (LRO) and short‐range ordering (SRO) below a Néel temperature of 26 K, while the SRO is retained at higher temperatures. The moments of the two independent Mn atoms lie in the bc plane, and that of Mn(1) rotates continuously by 54° towards the c axis on decreasing the temperature from 25 to 1.4 K. While the SRO may be associated with frustration of the moments within a Mn3 trimer, the LRO is achieved by antiparallel alignment of the four symmetry‐related trimers within the magnetic unit cell. A spin‐flop field, measured by dc and ac magnetization on a SQUID, is observed at 15 kOe.</abstract><abstract lang="fr">[Mn3(OH)2(SO4)2(H2O)2] et son équivalent deutérié ont été préparés par synthèse hydrothermale et caractérisés par ATG‐ATD et spectroscopie infrarouge. Sa structure, affinée à partir de données de diffraction RX sur monocristal, est analogue à celle du sel de nickel correspondant et fait apparaître un réseau 3D formé par des chaînes d′octaèdres Mn(1)O6 liés par une arête, chaînes connectées entre elles par un sommet commun à des octaèdres Mn(2)O6 et des tétraèdres SO4. La détermination de la structure magnétique et les mesures des propriétés magnétiques et de chaleur spécifique indiquent la coexistence d′un ordre magnétique à longue distance (LRO) et à courte distance (SRO) en‐dessous de la température de Néel TN de 26 K, l′ordre à courte distance s′établissant à plus haute température. Les moments magnétiques des deux atomes Mn indépendants se trouvent dans le plan bc. Alors que celui de Mn(2) est toujours dirigé selon l′axe c, celui de Mn(1) se rapproche progressivement de cette direction lorsque la température est abaissée de TN à 1,4 K, la rotation globale étant de 54°. Alors que l′ordre à courte distance peut être dû à la frustation des moments à l′intérieur des trimères Mn3, en interaction antiferromagnétique, l′ordre à longue distance résulte de l′alignement antiparallèle des quatre trimères de la maille magnétique. Un champ de spin‐flop, mesuré par aimantation dc et ac, est observé à 15 kOe.</abstract><abstract>Both long‐ and short‐range magnetic ordering below its Néel temperature of 26 K are exhibited by [Mn3(OH)2(SO4)2(H2O)2], which was obtained by hydrothermal synthesis and characterized by X‐ray and neutron diffraction. The crystal structure consists of a three‐dimensional arrangement of MnO6, μ3‐OH, and μ4‐SO4 units. In the magnetic structure (see picture), the moments lie in the bc plane, and the moment of Mn(1) rotates from 74 to 20° with respect to the c axis on cooling from 26 to 1.4 K, while that of Mn(2) remains along the c axis.</abstract><subject lang="en"><genre>keywords</genre><topic>hydrothermal synthesis</topic><topic>hydroxide sulfates</topic><topic>magnetic properties</topic><topic>manganese</topic></subject><relatedItem type="host"><titleInfo><title>Chemistry – A European Journal</title></titleInfo><titleInfo type="abbreviated"><title>Chemistry – A European Journal</title></titleInfo><genre type="journal">journal</genre><note type="content"> Supporting information for this article is available on the WWW under http://www.wiley‐vch.de/contents/jc_2111/2004/f5645_s.pdf or from the author.</note><subject><genre>article-category</genre><topic>Full Paper</topic></subject><identifier type="ISSN">0947-6539</identifier><identifier type="eISSN">1521-3765</identifier><identifier type="DOI">10.1002/(ISSN)1521-3765</identifier><identifier type="PublisherID">CHEM</identifier><part><date>2004</date><detail type="volume"><caption>vol.</caption><number>10</number></detail><detail type="issue"><caption>no.</caption><number>8</number></detail><extent unit="pages"><start>2048</start><end>2057</end><total>10</total></extent></part></relatedItem><identifier type="istex">EC88300ECDF9D384AE6091F55E31582693F09D9A</identifier><identifier type="DOI">10.1002/chem.200305645</identifier><identifier type="ArticleID">CHEM200305645</identifier><accessCondition type="use and reproduction" contentType="copyright">Copyright © 2004 WILEY‐VCH Verlag GmbH & Co. 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