Three New Lanthanum Oxoantimonate(III) Halides: Synthesis and Crystal Structure of La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub>, La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>Br<sub>4</sub> and La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>I<sub>4</sub>

Three New Lanthanum Oxoantimonate(III) Halides: Synthesis and Crystal Structure of La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub>, La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>Br<sub>4</sub> and La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>I<sub>4</sub>

It was possible to synthesize colorless single crystals of La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub> (block-shaped) as well as La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>Br<sub>4</sub> and...

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Main Authors: Ralf J. C. Locke, Kim-Natalie Bozenhardt, Felix C. Goerigk, Thomas Schleid
Format: Article
Language:English
Published: MDPI AG 2023-04-01
Series:Crystals
Subjects:
lanthanum
oxoantimonates(III)
halides
crystal structures
Raman spectra
Online Access:https://www.mdpi.com/2073-4352/13/5/731
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author Ralf J. C. Locke
Kim-Natalie Bozenhardt
Felix C. Goerigk
Thomas Schleid
author_facet Ralf J. C. Locke
Kim-Natalie Bozenhardt
Felix C. Goerigk
Thomas Schleid
author_sort Ralf J. C. Locke
collection DOAJ
description It was possible to synthesize colorless single crystals of La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub> (block-shaped) as well as La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>Br<sub>4</sub> and La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>I<sub>4</sub> (both needle-shaped), representing three new compounds from the system of lanthanum oxoantimonate(III) halides, which have not been described in the literature before. La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub> crystallizes in the monoclinic space group <i>P</i>2/<i>c</i> with the lattice parameters <i>a</i> = 895.82(5) pm, <i>b</i> = 564.28(3) pm, <i>c</i> = 1728.19(9) pm, and <i>β</i> = 90.007(2)° for <i>Z</i> = 2. This layered compound contains isolated ψ<sup>1</sup>-tetrahedral [SbO<sub>3</sub>]<sup>3–</sup> units, square hemiprisms [LaO<sub>8</sub>]<sup>13–</sup>, and antiprisms [LaO<sub>4</sub>Cl<sub>4</sub>]<sup>9−</sup>. La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>Br<sub>4</sub> and La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>I<sub>4</sub> crystallize isotypically in the orthorhombic space group <i>Pnma</i> with <i>a</i> = 3184.69(19) pm, <i>b</i> = 417.78(3) pm, <i>c</i> = 1019.85(6) pm for the bromide and <i>a</i> = 3215.08(19) pm, <i>b</i> = 419.94(3) pm, <i>c</i> = 1062.89(6) pm for the iodide. Instead of isolated [SbO<sub>3</sub>]<sup>3−</sup> anions, semi-tubular features <inline-formula><math display="inline"><semantics><mrow><mtable><mtr><mtd><mn>1</mn></mtd></mtr><mtr><mtd><mo>∞</mo></mtd></mtr></mtable></mrow></semantics></math></inline-formula>{[Sb<sub>12</sub>O<sub>19</sub>]<sup>2−</sup>} are present, which consist mainly of [SbO<sub>4</sub>]<sup>5−</sup> and few [SbO<sub>3</sub>]<sup>3−</sup> units with stereochemically active electronic lone pairs at their Sb<sup>3+</sup> centers. Within these so-called “double-halfpipes”, La<sup>3+</sup> is surrounded by nine oxygen atoms as [LaO<sub>9</sub>]<sup>15–</sup> polyhedron without any contact with <i>X</i><sup>−</sup> anions. Single-crystal Raman measurements were performed for La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub> and La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>I<sub>4</sub>, and La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub> was structurally compared with the isostoichiometric, but not isotypic La<sub>5</sub>F<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub>.
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spelling doaj.art-e2200bb59dcc47c5be3da1897ed1240e2023-11-18T00:59:05ZengMDPI AGCrystals2073-43522023-04-0113573110.3390/cryst13050731Three New Lanthanum Oxoantimonate(III) Halides: Synthesis and Crystal Structure of La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub>, La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>Br<sub>4</sub> and La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>I<sub>4</sub>Ralf J. C. Locke0Kim-Natalie Bozenhardt1Felix C. Goerigk2Thomas Schleid3Institute for Inorganic Chemistry, University of Stuttgart, D-70569 Stuttgart, GermanyInstitute for Inorganic Chemistry, University of Stuttgart, D-70569 Stuttgart, GermanyInstitute for Inorganic Chemistry, University of Stuttgart, D-70569 Stuttgart, GermanyInstitute for Inorganic Chemistry, University of Stuttgart, D-70569 Stuttgart, GermanyIt was possible to synthesize colorless single crystals of La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub> (block-shaped) as well as La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>Br<sub>4</sub> and La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>I<sub>4</sub> (both needle-shaped), representing three new compounds from the system of lanthanum oxoantimonate(III) halides, which have not been described in the literature before. La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub> crystallizes in the monoclinic space group <i>P</i>2/<i>c</i> with the lattice parameters <i>a</i> = 895.82(5) pm, <i>b</i> = 564.28(3) pm, <i>c</i> = 1728.19(9) pm, and <i>β</i> = 90.007(2)° for <i>Z</i> = 2. This layered compound contains isolated ψ<sup>1</sup>-tetrahedral [SbO<sub>3</sub>]<sup>3–</sup> units, square hemiprisms [LaO<sub>8</sub>]<sup>13–</sup>, and antiprisms [LaO<sub>4</sub>Cl<sub>4</sub>]<sup>9−</sup>. La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>Br<sub>4</sub> and La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>I<sub>4</sub> crystallize isotypically in the orthorhombic space group <i>Pnma</i> with <i>a</i> = 3184.69(19) pm, <i>b</i> = 417.78(3) pm, <i>c</i> = 1019.85(6) pm for the bromide and <i>a</i> = 3215.08(19) pm, <i>b</i> = 419.94(3) pm, <i>c</i> = 1062.89(6) pm for the iodide. Instead of isolated [SbO<sub>3</sub>]<sup>3−</sup> anions, semi-tubular features <inline-formula><math display="inline"><semantics><mrow><mtable><mtr><mtd><mn>1</mn></mtd></mtr><mtr><mtd><mo>∞</mo></mtd></mtr></mtable></mrow></semantics></math></inline-formula>{[Sb<sub>12</sub>O<sub>19</sub>]<sup>2−</sup>} are present, which consist mainly of [SbO<sub>4</sub>]<sup>5−</sup> and few [SbO<sub>3</sub>]<sup>3−</sup> units with stereochemically active electronic lone pairs at their Sb<sup>3+</sup> centers. Within these so-called “double-halfpipes”, La<sup>3+</sup> is surrounded by nine oxygen atoms as [LaO<sub>9</sub>]<sup>15–</sup> polyhedron without any contact with <i>X</i><sup>−</sup> anions. Single-crystal Raman measurements were performed for La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub> and La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>I<sub>4</sub>, and La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub> was structurally compared with the isostoichiometric, but not isotypic La<sub>5</sub>F<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub>.https://www.mdpi.com/2073-4352/13/5/731lanthanumoxoantimonates(III)halidescrystal structuresRaman spectra
spellingShingle Ralf J. C. Locke
Kim-Natalie Bozenhardt
Felix C. Goerigk
Thomas Schleid
Three New Lanthanum Oxoantimonate(III) Halides: Synthesis and Crystal Structure of La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub>, La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>Br<sub>4</sub> and La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>I<sub>4</sub>
Crystals
lanthanum
oxoantimonates(III)
halides
crystal structures
Raman spectra
title Three New Lanthanum Oxoantimonate(III) Halides: Synthesis and Crystal Structure of La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub>, La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>Br<sub>4</sub> and La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>I<sub>4</sub>
title_full Three New Lanthanum Oxoantimonate(III) Halides: Synthesis and Crystal Structure of La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub>, La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>Br<sub>4</sub> and La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>I<sub>4</sub>
title_fullStr Three New Lanthanum Oxoantimonate(III) Halides: Synthesis and Crystal Structure of La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub>, La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>Br<sub>4</sub> and La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>I<sub>4</sub>
title_full_unstemmed Three New Lanthanum Oxoantimonate(III) Halides: Synthesis and Crystal Structure of La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub>, La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>Br<sub>4</sub> and La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>I<sub>4</sub>
title_short Three New Lanthanum Oxoantimonate(III) Halides: Synthesis and Crystal Structure of La<sub>5</sub>Cl<sub>3</sub>[SbO<sub>3</sub>]<sub>4</sub>, La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>Br<sub>4</sub> and La<sub>2</sub>Sb<sub>12</sub>O<sub>19</sub>I<sub>4</sub>
title_sort three new lanthanum oxoantimonate iii halides synthesis and crystal structure of la sub 5 sub cl sub 3 sub sbo sub 3 sub sub 4 sub la sub 2 sub sb sub 12 sub o sub 19 sub br sub 4 sub and la sub 2 sub sb sub 12 sub o sub 19 sub i sub 4 sub
topic lanthanum
oxoantimonates(III)
halides
crystal structures
Raman spectra
url https://www.mdpi.com/2073-4352/13/5/731
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