ISSN:
0044-2313
Keywords:
Tetraphenylphosphonium thiohalogenoarsenate(III)
;
pentathiacyclothioarsenate(III)
;
synthesis
;
crystal structures
;
Chemistry
;
Inorganic Chemistry
Source:
Wiley InterScience Backfile Collection 1832-2000
Topics:
Chemistry and Pharmacology
Description / Table of Contents:
Novel Routes to the Synthesis of Thiohalogeno- and Cyclothioarsenates(III). Crystal Structures of PPh4[As2SBr6] · CH3CN and PPh4[SAsS5]By reactions of (PPh4)2[As2Cl8] and (PPh4)2[As2Br8] with Na2S4 in acetonitrile (PPh4)2[As2SCl6] · CH3CN and (PPh4)2[As2SBr6] · CH3CN were obtained, respectively. Using K2S5, PPh4[As2SCl5] and PPh4[SAsS5] were the products. The latter can also be obtained from PPh4[As2SCl5] and Na2S4, while PPh4[As3S3Br4] is formed from PPh4[As2SBr5] with K2S5. Two X-ray crystal structure determinations were performed. PPh4[As2SBr6] · CH3CN: triclinic, P1, Z = 2, a = 1200.4(7), b = 1507.3(6), c = 1594.4(8) pm, α = 81.59(2), β = 78.22(3), γ = 80.58(2)°, R = 0.096 for 2298 observed reflexions. The structure contains [As2SBr6]2- -ions in which the two Sb atoms are joined via one S and two Br atoms. PPh4[SAsS5]: triclinic, P1, Z = 2, a = 1133.9(4), b = 1142.5(4), c = 1186.9(5) pm, α = 102.77(4), β = 107.74(3), γ = 106.65(3)°, R = 0.043 für 2677 reflexions. In the [SAsS5]- -ion an AsS5 ring in the chair conformation is present.
Notes:
Durch Reaktionen von (PPh4)2[As2Cl8] und (PPh4)2[As2Br8] mit Na2S4 in Acetonitril wurden (PPh4)2[As2SCl6] · CH3CN bzw. (PPh4)2[As2SBr6] · CH3CN hergestellt. Mit K2S5 entstanden PPh4[As2SCl5] bzw. PPh4[SAsS5]. Letzteres ist auch aus PPh4[As2SCl5] und Na2S4 zugänglich, während PPh4[As3S3Br4] aus PPh4[As2SBr5] mit K2S5 entsteht. Zwei Kristallstrukturen wurden durch Röntgenbeugung bestimmt.PPh4[As2SBr6] · CH3CN: triklin, P1, Z = 2, a = 1200,4(7), b = 1507,3(6), c = 1594,4(8) pm, α = 81,59(2), β = 78,22(3), γ = 80,58(2)°. R = 9,6% für 2298 beobachtete Reflexe. Die Struktur enthält [As2SBr6]2- - Ionen, in denen die beiden Sb-Atome über ein S- und zwei Br-Atome miteinander verbunden sind. PPh4[SAsS5]: triklin, P1, Z = 2, a = 1133,9(4), b = 1142,5(4), c = 1186,9(5) pm, α = 102,77(4), β = 107,74(3), γ = 106,65(3)°, R = 4,3% für 2677 Reflexe. Im [SAsS5]- -Ion ist ein AsS5-Ring in Sesselkonformation vorhanden.
Additional Material:
4 Ill.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1002/zaac.19926090316
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