| Abstract: | Metal Salts of Benzene‐1,2‐di(sulfonyl)amine. 3. Crystal Structures of the Free Protonated Ligand HN(SO2)2C6H4 (= HZ) and the Lamellar Cesium Salt CsZ Benzene‐1,2‐di(sulfonyl)amine ( 1 ; HZ), known since 1921, is a very strong NH acid and readily reacts with aqueous CsCl to form crystalline CsZ ( 3 ). For both compounds, crystal structures were determined by X‐ray diffraction at –100 °C ( 1 : monoclinic, space group P21/n, Z = 4; 3 : orthorhombic, Cmcm, Z = 4). In 1 , the five‐membered 1,3,2‐dithiazole heterocycle possesses an envelope conformation, the N atom lying 29.4(2) pm outside the mean plane of the S–C–C–S moiety S–N 167.06(15) and 167.53(15) pm, S–N–S 114.57(8)°]. In the crystal, HZ molecules are linked into chains by a conventional N–H…O hydrogen bond and further associated via four weak C–H…O bonds to form a three‐dimensional network. The conjugate Z⊖ ion in the layered structure of the salt 3 displays crystallographic C2v symmetry, leading to an ideally planar bicyclic framework S–N 158.29(15) pm, S–N–S 116.53(17)°]. Each of the five electronegative atoms bridges two cations, Cs⊕ attaining a tenfold coordination by forming bonds to two (O,N,O)‐chelating and four κ1O‐monodentate ligands. The Cs–O/N interactions create a polar CsN(SO2)2]∞ lamella, which is lipophilically wrapped by parallel benzo rings protruding perpendicularly from its surfaces. In contrast to the previously reported lamellar metal di(arenesulfonyl)amides, the aromatic groups pertaining to adjacent layers of 3 are seen to be markedly interlocked. |
