Die Reihe der nicht-zentrosymmetrischen tetragonalen Lanthanoid(III)-Oxidoantimonat(III)-Chloride LnSb2O4Cl (Ln = Gd–Lu)
Author:
Locke Ralf J. C.1, Goerigk Felix C.1, Schleid Thomas1
Affiliation:
1. Institut für Anorganische Chemie , Universität Stuttgart , Pfaffenwaldring 55, 70569 , Stuttgart , Deutschland
Abstract
Abstract
All representatives of the isotypic series LnSb2O4Cl (Ln = Gd–Lu) could be obtained as single crystals, which crystallize just like the prototypic YSb2O4Cl in the non-centrosymmetric tetragonal space group P4212. The steady decrease in lattice parameters from a = 781.08(4) pm and c = 881.47(6) pm for GdSb2O4Cl to a = 764.66(4) pm and c = 877.53(7) pm for LuSb2O4Cl reflect the consequences of the lanthanide contraction, as expected. The Ln
3+ cations reside in the surrounding of eight oxygen atoms arranged as square hemiprisms [LnO8]13−, which are linked by four of their coplanar edges to form layers according to
2
∞
{
[
L
n
O
8
/
2
e
]
5
−
}
$\begin{array}{l}2\hfill \\ \infty \hfill \end{array}\left\{{\left[Ln{\text{O}}_{8/2}^{e}\right]}^{5-}\right\}$
parallel to the (001) plane. The Sb3+ cations form ψ1-tetrahedral [SbO3]3– anions together with three oxygen atoms. Two of these anions are connected with additional Sb3+ cations, but the third one shows no extra connectivity. Four ψ1-tetrahedral [SbO3]3– units build an eight-membered ring
0
∞
{
[
Sb
4
O
8
]
4
−
}
$\begin{array}{l}0\hfill \\ \infty \hfill \end{array}\left\{{\left[{\text{Sb}}_{4}{\text{O}}_{8}\right]}^{4-}\right\}$
. These isolated rings are arranged parallel to the (001) plane. Between the oxygen-connected triple layers of Ln
3+ and Sb3+ cations with the composition
2
∞
{
[
L
n
Sb
2
O
4
]
+
}
$\begin{array}{l}2\hfill \\ \infty \hfill \end{array}\left\{{\left[Ln{\text{Sb}}_{2}{\text{O}}_{4}\right]}^{+}\right\}$
there are single layers of Cl− anions, not connected strongly to any of the trications. Due to the presence of isolated cyclic [Sb4O8]4– anions, these lanthanoid(III) oxidoantimonate(III) chlorides LnSb2O4Cl (Z = 4) can also be described with the molecular formula Ln
2[Sb4O8]Cl2 (Ln = Gd–Lu) for Z = 2.
Publisher
Walter de Gruyter GmbH
Subject
General Chemistry
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