Darstellung und Kristallstruktur von Ethylendiammonium‐Selenostannaten(IV) sowie von [2 SnSe₂ · en]_∞

Abstract

Die Selenostannate(IV) [enH2]2[Sn2Se6] · 1/2 en 1 und [enH2][Sn3Se7] · 1/2en 2 wurden durch methanolothermale Reaktion von SnSe2 mit Ethylendiamin (en) (160°C, 13 bar) in Anwesenheit von Se bzw. BaSe dargestellt. Das Anion [Sn2Se6]4− in 1 besteht aus zwei kantenverknüpften SnSe4‐Tetraedern und weist kristallographische Ci‐Symmetrie auf. Im Kristallgitter von 2 liegen schichtartige Polyanionen [Sn3Se72] ∞2 vor, die trigonale SnSe5‐Bipyramiden als Baueinheiten aufweisen. Die drei symmetrieunabhängigen Zinnatome sind jeweils über SnSeSnBrücken miteinander verknüpft, so daß Sn3Se10‐Einheiten entstehen. Die methanolothermale Umsetzung von SnSe2 mit en allein liefert die kantenverknüpfte Kettenstruktur [2 SnSe2 · en]∞ 3, in der die Zinnatome jeweils von vier Selenatomen koordiniert sind. Jedes zweite Zinnatom wird zusätzlich von einem en‐Molekül koordiniert und weist somit eine verzerrte oktaedrische Geometrie auf. Die restlichen Zinnatome sind tetraedrisch von Se‐Atomen umgeben.

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“…Tetramethylammoniumhydroxid [10,11], Ethylendiamin [12] und Triethylentetramin [13] Die u È berwiegende Mehrzahl der Wasserstoffatome konnte ebenfalls lokalisiert werden, wurde jedoch an geometrisch sinnvolle Positionen gesetzt. Geburtstag gewidmet.…”

Synthesis and Structure of [Sn4Se11]6-,1∞ [Sn2Se52-], and1∞ [Sn3Se72-] - Model Anions for the Solventothermal Reaction Pathway to Lamellar Selenidostannates(IV)

“…Reaction of A 2 CO 3 (A = K, Rb) with Sn and Se in an H 2 O/CH 3 OH mixture at 115±130°C affords the isotypic selenidostannates(IV) A 6 Sn 4 Se 11´x H 2 O (A = K, x = 8) 1 and 2 whose discrete [Sn 4 Se 11 ] 6± anions each contain two corner-bridged ditetrahedral [Sn 2 Se 6 ] 4± species. Similar reaction conditions with A = Cs afford Cs 2 Sn 2 Se 5´H2 O (3 a) and Cs 2 Sn 2 Se 5 (3 b) [3,4], increased interest in possible ion exchange, molecular recognition and optoelectronic applications of such lamellar chalcogenidostannates(IV) has led to a flurry of structural and physical studies on this class of compounds in the past four years [5]. The first discussion of the technological potential of 2-and 3-dimensional polymeric thio-and selenidometalates(IV) of the heavier Group 14 elements Ge and Sn as zeotype materials appeared in an article by Bedard et al in 1989 [6].…”

“…The generation of chalcogenidostannates(IV) of the type A 2 Sn 3 E 7 (E = S, Se) by a wide variety of structure-directing cations A + with different shapes and sizes (E = S, A = Me 4 N [8], Me 3 NH [12], NH 4 , Et 4 N, nPr 3 NH, tBuNH 3 [9], dabcoH [13], dabco = 1,4-diazabicyclo[2.2.2]-octane; E = Se, A = Cs [12] Me 2 NH 2 [3,4]) appears to be a consequence of the remarkable flexibility and stacking variability of their component 2 ∞ [Sn 3 S 7 2± ] sheets. Not surprisingly, this has led to studies of the ion exchange properties [8] and reversible molecule discriminating optical and electrical responses [14] of these nanoporous semiconductors.…”

Solventothermal Synthesis of the Lamellar Selenidostannates(IV) A2Sn4Se9 · H2O (A = Rb, Cs) and Cs2Sn2Se6

“…In contrast to the lamellar thiostannates(IV), synthetic and structural studies on the analogous selenidostannates(IV) are still surprisingly lim ited [4,5,7]. However, Ozin et al have recently demonstrated that the absorption edges for the mixed compounds ( I V^N^t S n^^S e i -^] exhibit a monotonous red shift as the selenium content is increased [15], thereby indicating a potential appli cation of this class of materials as tuneable semi conductors.…”

“…Following our initial reports on the synthesis and structure of the prototypes Cs4Sn5Si2-2 H20 [3], Cs2Sn3Se7 [4], (Me2NH2)2Sn3Se7 [5] and * Reprint requests to Prof. Dr. W. S. Sheldrick. (enH2)2Sn3Se7 0.5en [5], increasing interest in the properties of these nanoporous materials has led to a flurry of structural and physical studies in the past three years. Potential technological appli cations of zeotype Group 14 thio-and selenidometalates appear to have been emphasized in depth for the first time in an article by Bedard et al in 1989 [6 ].…”