Die Kristallstruktur von Kalium‐trithiowolframat‐chlorid K₃(WOS₃)Cl

Abstract

Eine aus chloridhaltigen Lösungen von K2WOS3 kürzlich neu dargestellte Phase wurde durch eine vollständige Röntgenstrukturanalyse als Doppelsalz aus äquimolaren Anteilen K2WOS3 und KCl charakterisiert. Raumgruppe: Pca21 mit a = 12,507 Å, b = 6,3171 Å, c = 12,371 Å, V = 977,4 Å3, Z = 4. Die als Trikaliumtrithiowolframat(VI)‐chlorid K3(WOS3)Cl zu formulierende Verbindung stellt einen bisher unbekannten Strukturtyp MI2XY4 · MIZ dar. Neben isolierten tetraedrischen WOS32‐‐Ionen (Bindungslängen W‐O: 1,760 Å, W–S: 2,208; 2.197; 2,196 Å) liegen von K+ verzerrt oktaedrisch koordinierte Cl‐Ionen und von 5S + 10 + 2Cl umgebene K+‐Ionen vor. Die Bindundgsparameter des WOS32−‐Ions zeigen, daß in Übereinstimmung mit anderen Chalkogeno‐anionen der Übergangsmetalle hohe π‐Bindungsanteile vorliegen. Daß die W–S‐Bindungen aber nicht vollständig am Bindungsausgleich beteiligt sind.

Ba6V4O5S11

“…number of O atoms in the tetrahedral coordination sphere increases is thought to be related to the 7rbonding abilities of oxygen as compared to sulfur, as has been noted elsewhere (Gardner, Fettinger & Eichhorn, 1994;Krebs, Buss & Ferwanah, 1972;Mtiller & Diemann, 1969). The four crystallographically distinct Ba 2+ ions are nine or ten coordinate with the following coordination environments: Ba(1)OS9, Ba(2)O3S6, Ba(3)O2S7, Ba(4)O4S5.…”

Competing hydrogen-bond acceptors in ethylenediammonium oxotrithiotungstate(VI)

“…A competing hydrogen-bond acceptor, such as oxygen in oxotrithiotungstate [WOS 3 ] 2À compounds, offers the possibility to investigate the occurrence of NÐHÁ Á ÁO as well as NÐHÁ Á ÁS interactions in the same compound. Although the synthetic aspects of [WOS 3 ] 2À (Mu È ller & Diemann, 1968;McDonald et al, 1983), spectral characteristics (Mu È ller et al, 1969(Mu È ller et al, , 1981, reactivity studies (Ansari et al, 1988) and medical applications (Mason et al, 1989) have been reported in the literature, only two structurally characterized monooxotrithiotungstates, namely K 3 [WOS 3 ]Cl (Krebs et al, 1972) and (pipH) 4 [WOS 3 ][WS 4 ] (pipH is piperidinium) (Siemeling et al, 2006), are known to date. Both reported compounds are double salts and contain Cl À or [WS 4 ] 2À anions in addition to [WOS 3 ] 2À in their structures.…”

Synthesis, Crystal Structure, and Optical Characterization of the Sulfide Chloride Oxide CsBa6V4S12ClO4 with a Near-Infrared Fluorescence

“…There are known compounds with similar S−Cl−O anion complexity: K 3 (WOS 3 )Cl contains a monocapped quasioctahedral KS 4 Cl 2 O coordination; 25 27 but with S/Cl disorder, making it difficult to determine the actual coordination situation. However, in none of those cases have the optical properties been measured yet.…”

“…There are known compounds with similar S–Cl–O anion complexity: K 3 (WOS 3 )Cl contains a monocapped quasi-octahedral KS 4 Cl 2 O coordination; RES 4 Cl 2 O (RE = La–Nd) contains distorted, monocapped facial coordination (1 + 7) of RE ions; and La 5 Ti 6 S 3 Cl 3 O 15 has two different La coordinations, fac -like La­(S/Cl) 6 O 4 and girdle-like La­(S/Cl) 6 O 6 , but with S/Cl disorder, making it difficult to determine the actual coordination situation. However, in none of those cases have the optical properties been measured yet.…”