Polysulfonylamine. CLXXVIII Onium‐Salze des Benzol‐1,2‐di(sulfonyl)amins (HZ): Eine zweite Kristallform des Ammonium‐Salzes NH 4 Z·H 2 O und Kristallstruktur des Bis(triphenylphosphoranyliden)ammonium‐Salzes [Ph 3 PNPPh 3 ]Z

• Published in: Zeitschrift für anorganische und allgemeine Chemie (1950) Vol. 633; no. 4; pp. 593 - 602
• Main Authors: Zerbe, Eva‐Maria, Wölper, Christoph, Roca Piñol, Silvia, Jones, Peter G., Blaschette, Armand
• Format: Journal Article
• Language: English
• Published: 01-04-2007
• ISSN: 0044-2313; 1521-3749
• DOI: 10.1002/zaac.200600352

Polysulfonylamines. CLXXVIII. Onium Salts of Benzene‐1,2‐di(sulfonyl)amine (HZ): A Second Crystal Form of the Ammonium Salt NH
4
Z·H
2
O and Crystal Structure of the Bis(triphenylphosphoranylidene)ammonium Salt [Ph
3
PNPPh
3
]Z
A dimorphic form of NH
4
Z·H
2
O, where Z
−
is N‐deprotonated
ortho
‐benzenedisulfonimide, has been obtained and structurally characterized (previously known form
1A
: monoclinic,
P
2
1
/
c
,
Z′
= 1; new polymorph
1B
: monoclinic,
P
2
1
/
n
,
Z′
= 1). Both structures are dominated by an abundance of classical hydrogen bonds N
+
–H/O–H···O=S/OH
2
, 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 [Ph
3
PNPPh
3
]Z (
2
, monoclinic,
P
2
1
/
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.