Sr₃(BS₃)₂ und Sr₃(B₃S₆)₂: Zwei neue nicht‐oxidische Chalkogenoborate mit trigonal‐planar koordiniertem Bor

Abstract

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.

BaM(BS3)S (M = Sb, Bi): Two New Thioborate Compounds with One-Dimensional Polymeric Chain Structure

“…The Ba 2+ cations have a typical coordination environment with nine sulfur atoms at distances of 3.162−3.3943 Å for BaSb(BS 3 )S and 3.2060−3.4023 Å for BaBi(BS 3 )S (Figure ). Boron atoms have typical trigonal plane coordinations with three sulfide atoms, and the bond lengths range from 1.770(4) to 1.818(2) Å for BaSb(BS 3 )S and 1.765(13) to 1.817(7) Å for BaBi(BS 3 )S, which are in accordance with values reported previously in the literature. ,, The bond angles of S−B−S slightly deviate away from 120° as a result of the asymmetrical coordination environment of [BS 3 ] 3− anions, while the sum of S−B−S bond angles is exactly equal to 360°, which indicates a planar [BS 3 ] 3− structure in both of the compounds, BaSb(BS 3 )S and BaBi(BS 3 )S.…”

“…A quartz glass ampule is usually employed in sulfide synthesis, but it will be attacked by boron sulfide owing to the latter’s high chemical reactivity, especially under high temperatures above 650 K. ,, When this happens, B−Si exchange will bring impurities of B 2 O 3 and SiS 2 and prevent further formation of thioborates . Accordingly, we adopt graphite crucibles as reagent containers in the following experiments.…”

HgB2S4: A d10 Metal Thioborate with Giant Birefringence and Wide Band Gap

“…Since the [B 3 S 6 ] unit is composed of three [BS 3 ] triangles, the [B 3 S 6 ] units should have larger polarization anisotropy, which may generate larger birefringence. Up to now, research about the microscopic properties of [B 3 S 6 ] units has not been performed, and the compounds with [B 3 S 6 ] as the building blocks − have also not been characterized. Therefore, systematical studies about the [B 3 S 6 ] units and new materials explorations are needed and meaningful.…”

Syntheses, Characterization, and Optical Properties of Centrosymmetric Ba3(BS3)1.5(MS3)0.5 and Noncentrosymmetric Ba3(BQ3)(SbQ3)

“…To date, only a relatively small number of thioborates are structurally determined because of the high chemical reactivity of boron sulfide, and most of them are centrosymmetric (CS). For example, seven ternary AE/B/S (AE = Ca, Sr, Ba) compounds are known as CaB 2 S 4 , SrB 2 S 4 , Sr 3 B 6 S 12 , Sr 3 B 2 S 6 , Sr 4.2 Ba 2.8 B 4 S 13 , BaB 2 S 4 , and Ba 7 B 4 S 13 ; among them BaB 2 S 4 is the only noncentrosymmetric (NCS) example. Similarly, very rare quaternary AE/B/M/S (M = transition or main group metals) compounds are known, and the only NCS compound Zn x Ba 2 B 2 S 5+ x ( x ≈ 0.2) exhibits a very weak second harmonic generation (SHG) efficiency (∼50 times greater than that of α-SiO 2 at 1.064 μm incident laser radiation) …”