Neue Synthesewege für Thiohalogeno‐ und Cyclothioarsenate(III). Kristallstrukturen von PPh₄[As₂SBr₆] · CH₃CN und PPh₄[SAsS₅]

Abstract

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.

Structural Diversity, Optical and Magnetic Properties of a Series of Manganese Thioarsenates with 1,10-Phenanthroline or 2,2′-Bipyridine Ligands: Using Monodentate Methylamine as an Alkalinity Regulator

“…Each Mn atoms in the {[Mn(2,2′-bipy) 2 ] 2 (As V S 4 )} + cation with a distorted octahedral geometry is six coordinated by four N atoms from two phen molecules and two S atoms from one (As V S 4 ) 3– anion. The As atoms show different coordination environments: As1 is coordinated by four S atoms to form a (As V S 4 ) 3– tetrahedron, while As2 is coordinated by one S atom and one S 5 unit to form a [As III S(S 5 )] − anion, which is rarely reported in the literature and belongs to the well-known group V chalcogenide anion family of [M III Q(Q x )] − ( x > 2). In 5 , there exist intercation face-to-face π···π stacking interactions between the aromatic rings of phen molecules with centroid–centroid distance varying from 3.478(1) to 3.811(1) Å and dihedral angles in the range of 0.00(13)–2.16(9) °, which link the polycations {[Mn(2,2′-bipy) 2 ] 2 (As V S 4 )} + into a 2-D extended layer structure parallel to the (111) plane (Supporting Information Figure S11a).…”

Synthesis and Crystal Structures of New Antimony Polysulfido Complexes: [P(C6H5)4]3Sb3S25 and [P(C6H5)4]2Sb2S15 · 2(C3N2H6)

“…Since polysulfides are versatile ligands they propose to be valuable molecular entities for the desired`open' structures. In contrast to the wealth of transition metal polysulfide complexes [6], only few examples are known for main group elements, including examples like Sn(S 4 ) 3 2± [7], Bi 2 S 34 4± [8] and SAsS 5 ± [9]. The majority of these molecular examples were prepared at ambient temperatures in aprotic solvents due to the higher activity of polysulfides in such solvents [10].…”