Polysulfonylamine. CLXXIV [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 17 [2] Silber(I)‐di(methansulfonyl)amid: Ein diamantoides Netzwerk aus Ag₂N₂‐Vierringen und verbrückenden Mesylgruppen

Abstract

The crystal structure of silver(I) dimesylamide (orthorhombic, space group Fddd, Z ϭ 16, ZЈ ϭ 1/2, single-crystal X-ray diffraction at Ϫ140°C) consists of dinuclear Ag 2 [N(SO 2 Me) 2 ] 2 complexes, in which the nitrogen atoms are µ 2 -bonded to the silver ions at distances of 241.83(15) pm to form planar rhombic Ag 2 N 2 rings; the short Ag···Ag ring diagonal, 285.36(4) pm, is consistent with weak argentophilic interaction. In the packing, the ring centres lie on 222 sites, conferring crystallographic D 2 symmetry on the complex and crystallographic C 2 symmetry on the anions. Moreover, each complex is connected to four adjacent complexes by centrosymmetric pairs of silver-oxygen bonds at distances 245.35(13) pm. In the resulting three-dimensional coordination

Argentophilic Interactions

“…Recent examples also include silver sulfonylamides, cyanoximates, or triazine complexes in which Ag-Ag contacts are supported by multiple Ag-O or Ag-N coordination. [167][168][169] While in earlier work these aspects had not been considered, any such arrangement shows up prominently now in the discussions of the bonding characteristics in the current literature.…”

“…These units are further connected in the same way through the terminal carboxylate groups at the substituents R to give a three-dimensional diamantoid network. [167,254] Another illustrative case is the hexanuclear complex [{Ag(CF 3 COO)} 6 ]·6 Ph 3 PS. The CF 3 COO groups are positioned alternately above and below the ring of silver atoms, and the average length of the six Ag-Ag contacts is 3.20 .…”

“…As mentioned in the Introduction, solid‐state chemistry provides many examples in which the combinations of silver cations and oxo‐ or imino‐anions lead to a multicontact pattern, but the role of argentophilic interactions in these systems is far from clear. Recent examples also include silver sulfonylamides, cyanoximates, or triazine complexes in which Ag–Ag contacts are supported by multiple Ag–O or Ag–N coordination 167–169. While in earlier work these aspects had not been considered, any such arrangement shows up prominently now in the discussions of the bonding characteristics in the current literature.…”

Argentophile Wechselwirkungen

“…Jüngste Beispiele schließen auch Sulfonylamid-, Cyanoximat-oder Triazinkomplexe mit ein, in denen Ag···Ag-Kontakte durch Ag-O-oder Ag-N-Mehrfachkoordination unterstützt werden. [167][168][169] Während diese Aspekte in früheren Arbeiten gar nicht in Betracht gezogen wurden, wird in der aktuellen Literatur bei der Diskussion der Bindungseigenschaften jede derartige Anordnung deutlich hervorgehoben.…”

“…[250] In früheren Arbeiten haben Pyrazin-und Pyrimidinliganden ähnliche Strukturergebnisse geliefert. [251] Mangan ( [167,254] Ein anderer illustrativer Fall ist der sechskernige Komplex [{Ag(CF 3 COO)} 6 ]·6 Ph 3 PS. Die CF 3 COO-Gruppen befinden sich abwechselnd ober-und unterhalb des Rings aus Silberatomen, und die sechs Ag···Ag-Kontakte sind durchschnittlich 3.20 lang.…”