Polysulfonylamine. CLXXVIII Onium‐Salze des Benzol‐1,2‐di(sulfonyl)amins (HZ): Eine zweite Kristallform des Ammonium‐Salzes NH₄Z·H₂O und Kristallstruktur des Bis(triphenylphosphoranyliden)ammonium‐Salzes [Ph₃PNPPh₃]Z

Abstract

Polysulfonylamines. CLXXVIII. Onium Salts of Benzene‐1,2‐di(sulfonyl)amine (HZ): A Second Crystal Form of the Ammonium Salt NH4Z·H2O and Crystal Structure of the Bis(triphenylphosphoranylidene)ammonium Salt [Ph3PNPPh3]ZA dimorphic form of NH4Z·H2O, where Z− is N‐deprotonated ortho‐benzenedisulfonimide, has been obtained and structurally characterized (previously known form 1A: monoclinic, P21/c, Z′ = 1; new polymorph 1B: monoclinic, P21/n, Z′ = 1). Both structures are dominated by an abundance of classical hydrogen bonds N+–H/O–H···O=S/OH2, whereby the anionic N− function does not act as an acceptor. The major difference between the dimorphs arises from the topology of the hydrogen bond network, which is two‐dimensional in 1A, leading to a packing of discrete lamellar layers, but three‐dimensional in 1B. Moreover, the latter network is reinforced by a set of weak C–H··O/N hydrogen bonds, whereas the layered structure of 1A displays only one independent C–H···O bond, providing a link between adjacent layers. The compound [Ph3PNPPh3]Z (2, monoclinic, P21/c, Z′ = 1) is the first structurally authenticated example of an ionic Z− derivative in which the cation contains neither metal bonding sites nor strong hydrogen bond donors. This structure exhibits columns of anions, surrounded by four parallel columns of cations, giving a square array. The large cations are associated into a three‐dimensional framework via weak C–H···C(π) interactions and an offset face‐to‐face phenyl interaction, while the anions occupy tunnels in this framework and are extensively bonded to the surrounding cations by C–H···O/N− hydrogen bonds and C–H···C(π) interactions.

Preparation and Characterization of Aryl or Heteroaryl(3-indolyl)methylium o-Benzenedisulfonimides

“…In fact the shorter hydrogen bonds involve the O(11) and O(12) atoms and NH(1) and CH(8) atoms of the same molecule (see Figure ) while the other oxygen atoms and N(2) form quite longer hydrogen bonds with different cations. Other salts, for example [NH 4 ]­[C 6 H 4 (SO 2 ) 2 N]·H 2 O and the structurally related [M]­[C 6 H 4 (SO 2 ) 2 N]·H 2 O­(M = K,Rb), show the same behavior. The hydrogen bonds are listed in Table .…”