High-pressure synthesis and crystal structures of the strontium oxogallates Sr2Ga2O5 and Sr5Ga6O14

Article abstract of DOI:10.1016/j.jssc.2015.04.016

Abstract High-pressure synthesis experiments in a piston-cylinder apparatus at 1.5 GPa/3.0 GPa and 1000°C resulted in the formation of single-crystals of Sr₂Ga₂O₅ and Sr₅Ga₆O₁₄, respectively. The structures of both compounds have been solved from single-crystal diffraction data sets using direct methods. The first compound is orthorhombic with space group type Pbca (a=10.0021(4) ?, b=9.601(4) ?, c=10.6700(4) ?, V=1024.6(4) ?³, M_r=394.68 u, Z=8, D_x=5.12 g/cm³) and belongs to the group of single layer gallates. Individual sheets are parallel to (0 0 1) and can be built from the condensation of unbranched vierer single chains running along [0 1 0]. The layers are characterized by the presence of four- and strongly elliptical eight-membered rings of corner connected tetrahedra in UUDD and UUUUDDDD conformation. Strontium atoms are sandwiched between the tetrahedral layers for charge compensation and are coordinated by six and seven oxygen ligands, respectively. Sr₂Ga₂O₅ is isotypic with several other double sulfides and selenides. To the best of our knowledge, it is the first example of an oxide with this structure type. From a structural point of view, Sr₅Ga₆O₁₄ is a phyllogallate as well. The crystal structure adopts the monoclinic space group P2₁/c (a=8.1426(3) ?, b=8.1803(3) ?, c=10.8755(4) ?, β=91.970(4)°V=723.98(5) ?³, M_r=1080.42 u, Z=2, D_x=4.96 g/cm³). Individual sheets extend along (0 0 1). Basic building units are unbranched dreier single chains parallel to [1 0 0]. The layers contain tertiary (Q³) und quaternary (Q⁴) connected [GaO₄]-tetrahedra in the ratio 2:1 resulting in a Ga:O ratio of 3:7 and the formation of exclusively five-membered rings. Linkage between adjacent tetrahedral sheets is provided by three symmetrically independent strontium ions which are surrounded by six to eight oxygen atoms. The layers in Sr₅Ga₆O₁₄ are similar to those observed in the melilite structure-type. Crystallochemical relationships between the present phases and other known compounds are discussed in detail.

Full text of DOI:10.1016/j.jssc.2015.04.016

Author's Accepted Manuscript
High-pressure synthesis and crystal struc-
tures of the strontium oxogallates Sr2Ga2O5
and Sr5Ga6O14
Volker Kahlenberg, Valerie Goettgens, Philipp
Mair, Daniela Schmidmair
www.elsevier.com/locate/jssc
PII:
S0022-4596(15)00149-8
http://dx.doi.org/10.1016/j.jssc.2015.04.016
YJSSC18869
DOI:
Reference:
To appear in: Journal of Solid State Chemistry
Received date: 24 January 2015
Revised date: 5 April 2015
Accepted date: 12 April 2015
Cite this article as: Volker Kahlenberg, Valerie Goettgens, Philipp Mair,
Daniela Schmidmair, High-pressure synthesis and crystal structures of the
strontium oxogallates Sr2Ga2O5 and Sr5Ga6O14, Journal of Solid State Chemistry,
http://dx.doi.org/10.1016/j.jssc.2015.04.016
This is a PDF file of an unedited manuscript that has been accepted for
publication. As a service to our customers we are providing this early version of
the manuscript. The manuscript will undergo copyediting, typesetting, and
review of the resulting galley proof before it is published in its final citable form.
Please note that during the production process errors may be discovered which
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28

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We report the crystal structures of two new strontium oxogallates with composition
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Both phases have been obtained in the course of high-pressure piston-cylinder
experiments performed at 1.5 and 3.0 GPa
The crystallochemical characteristics and similarities with known structure types are
discussed in detail
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29