ISSN:
0044-2313
Keywords:
[Dibenzo-18crown6] · CH3CN · CH3CSOH
;
[Dicyclohexyl-18-crown6] · (CH3CSOH)2
;
[Cs(benzo-15crown5)2] CH3CSS
;
[Cs(dibenzo-18crown6)]2S5(DMF)2
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Synthesis and Crystal Structure of the Adducts [DB-18C6] · CH3CN · CH3CSOH and [DC-18C6](CH3CSOH)2 as well as of the Salt-like Compounds [Cs(B-15C5)2]CH3CSS and [Cs(DB-18C6)]2S5(DMF)21)The reaction products of crown ethers, cesium, and sulfur in aprotic solvents like acetonitrile and dimethylformamide strongly depend on the reaction conditions. Using CH3CN as a solvent, sometimes neutral host-guest adducts crystallize only, e.g., [dibenzo-18C6] · CH3CN · CH3CSOH (monoclinic, S. G. P21/c, Z = 4, a = 9.73(1) Å, b = 22.03(1) Å, c = 11.86(1) Å, β = 91.8(1)°) or [dicyclohexyl-18C6](CH3CSOH)2 (monoclinic, S. G. P21/n, Z = 2, a = 7.75(1) Å, b = 10.32(1) Å, c = 17.73(1) Å, β = 95.7(1)°). The monothioacetic acid, CH3CSOH, must be regarded as the first product of the hydrolysis of CH3CN. Furthermore, another product of this kind of hydrolysis, CH3CSSH, is obtained too. Therefore, we also obtain the salt-like compound [Cs(benzo-15C5)2]CH3CSS (monoclinic, S. G. C2/c, Z = 4, a = 16.05(1) Å, b = 16.73(1) Å, c = 13.11(1) Å, β = 106.3(1)°). If the solvent DMF is used, the pentasulfide [Cs(dibenzo-18C6)]2S5(DMF)2 crystallizes (monoclinic, S. G. P21/n, Z = 4, a = 14.79(1) Å, b = 14.24(1) Å, c = 25.74(1) Å, β = 92.7(1°. The S52- anions show the cis-conformation.
Notes:
Setzt man Kronenether mit Cs2CO3 im Molverhältnis 2:1 mit Schwefel und H2S in Dimethylformamid oder Acetonitril als Lösungsmitteln um, erhält man je nach Reaktionsführung und Lösungsmittel unterschiedliche Produkte. Mit Dibenzo-18-Krone-6 in CH3CN kristallisiert das neutrale 1:2-Addukt [Dibenzo-18C6] · CH3CSOH · CH3CN (monoklin, Raumgruppe P21/c, Z = 4; a = 9,73(1) Å; b = 22,03(1) Å; c = 11,86(1) Å; β = 91,8(1)°). Mit Dicyclohexyl-18-Krone-6 in CH3CN erhalten wir unter ähnlichen Bedingungen das neutrale 1:2-Addukt [Dicyclohexyl-18C6](CH3CSOH)2 (monoklin, Raumgruppe P21/n; Z = 2; a = 7,75(1) Å; b = 10,32(1) Å; c = 17,73(1) Å; β = 95,7(1)°). Mit Benzo-15-Krone-5 in CH3CN erhalten wir unter wiederum nicht wesentlich unterschiedlichen Bedingungen das Dithioacetat [Cs(Benzo-15C5)2]CH3CSS, das ein komplexes Kronenether-Kation aufweist (monoklin, Raumgruppe C2/c; Z = 4; a = 16,05(1) Å; b = 16,73(1) Å; c = 13,11(1) Å; β = 106,3(1)°). Wird Dibenzo-18-Krone-6 in DMF umgesetzt, kristallisiert das Pentasulfid [Cs(Dibenzo-18C6)]2S5(DMF)2 (monoklin, Raumgruppe P21/n; Z = 4; a = 14,79(1) Å; b = 14,24(1) Å; c = 25,74(1) Å; β = 92,7(1)°). Die Pentasulfid-Anionen sind cis-konformiert.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19966220414
Permalink
