Inhaltsübersicht. Bislang kennt man das Auftreten von sowohl trigonal-planar als auch tetraedrisch koordiniertem Bor in einer Kristallstruktur nur aus der Bor-Sauerstoff-Chemie. Mit dem neuen Bariummetathioborat BaB 2 S 4 stellen wir nun zum erstenmal eine Verbindung vor, deren Anionenstruktur aus zu Ketten kondensierten BS 3 -und BS 4 -Einheiten im Verhältnis 1 : 1 besteht, die entlang
BaB 2 S 4 : The first non-oxidic Chalcogenoborate with Boron in a trigonal-planar and tetrahedral CoordinationAbstract. Hitherto we know boron in a trigonal-planar and a tetrahedral coordination within one crystal structure from boron oxides in various compounds. With the novel bariummetathioborate BaB 2 S 4 we now report a crystal structure containing BS 3 and BS 4 units in the ratio 1 : 1 forming infinite chains along [001]. BaB 2 S 4 was synthesized in a solid state reaction at a temperature of 800°C from barium sulfide, amorphous boron and sulfur and crystallizes Einleitung
Systematic studies on selenoborates containing a B12 cluster entity and alkali metal cations led to the new crystalline phase K8[B12(BSe3)6] which consists of a icosahedral B12 cluster completely saturated with trigonal‐planar BSe3 units and potassium counter‐ions. For the first time three different anion substitution patterns are observed in one crystal structure. The new chalcogenoborate was prepared in a solid state reaction from potassium selenide, amorphous boron and selenium in evacuated carbon coated silica tubes at a temperature of 850 °C. K8[B12(BSe3)6] crystallizes in the monoclinic space group Cm (no. 8) with a = 16.288(2)Å, b = 41.617(4)Å, c = 9.788(1)Å, β = 109.59(1)°, and Z = 6.
Systematic studies on selenoborates containing a B12 cluster entity and alkali metal cations led to the new crystalline phase Na2[B18Se16] which consists of a icosahedral B12 cluster completely saturated with trigonal‐planar BSe3 units and sodium counter‐ions. The cluster entities are connected to each other via seleno‐ and perselenobridges. Thus a three‐dimensional network results with [(B18Se12Se6/2)n]2−‐ and [(B18Se15Se6/2)n]2− anions in a ratio of 2:1. The new chalcogenoborate was prepared in a solid state reaction from sodium selenide, amorphous boron and selenium in evacuated carbon coated silica tubes at a temperature of 850 °C. Na2[B18Se16] crystallizes in the trigonal space group ${\rm P}{\bar 3}$ (no. 147) with a = 17.021(1) Å, c = 8.903(1) Å and Z = 3.
Systematische Studien zur Synthese neuer Erdalkalimetallthioborate und zum Kationeneinfluß auf die Strukturen ternärer Verbindungen dieses Typs führten zu den Strontiumthioboraten Sr3(BS3)2 und Sr3(B3S6)2. Die neuen Verbindungen wurden aus Strontiumsulfid, amorphem Bor und Schwefel in Festkörperreaktionen bei einer Temperatur von 1123 K dargestellt. Die Kristallstrukturen wurden durch Röntgenstrukturanalysen an Einkristallen bestimmt. Sr3(BS3)2 kristallisiert in der monoklinen Raumgruppe C2/c (Nr. 15) mit a = 10, 187(4) Å, b = 6, 610(2) Å, c = 15, 411(7) Å, β = 102, 24(3)° und Z = 4. Die Kristallstruktur von Sr3(B3S6)2 ist trigonal, Raumgruppe R3¯ (Nr. 148), mit a = 8, 605(1) Å, c = 21, 542(4) Å und Z = 3. Sr3(BS3)2 enthält isolierte [BS3]3—‐Anionen mit Bor in trigonal‐planarer Koordination. Die Strontiumkationen befinden sich zwischen Schichten von Orthothioborat‐Anionen. Im Sr3(B3S6)2 liegen neben Strontiumkationen [B3S6]3—‐Anionen vor.
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