Polysulfonylamine. CLVIII [1] Kristallstrukturen von Metall‐di(methansulfonyl)amiden. 9 [2] Erhöhung der Kristallsymmetrie durch Kokristallisation: Monoklines Na[(CH3SO2)2N]·H2O und tetragonales NaK[(CH3SO2)2N]2·2H2O

Polysulfonylamines. CLVIII. Crystal Structures of Metal Di(methanesulfonyl)amides. 9. Enhancing Crystal Symmetry by Co‐crystallization: Monoclinic Na(CH₃SO₂)₂N]·H₂O and Tetragonal NaK(CH₃SO₂)₂N]₂·2H₂O The three‐dimensional coordination polymers NaA·H₂O ( 1 ) and NaKA₂·2H₂O ( 2 ), derived from the strong NH acid (MeSO₂)₂NH = HA, have been characterized by single crystal X‐ray diffraction at —95 °C ( 1 : monoclinic, space group C2/c, Z′ = 2; 2 : tetragonal, P4₃2₁2, Z′ = 1). The results suggest that structures with Z′ > 1 are good candidates for co‐crystallization experiments. Both packings display layer substructures built up from the multidentately coordinating anions, the aquo ligands and two kinds of chemically and/or crystallographically distinct cations, whereas cations of a third type are intercalated between the layers. All anions have the extended standard conformation of this species; 1 contains two pseudo‐C₂ symmetric A^—, 2 one pseudo‐C₂ and two crystallographically C₂ symmetric A^—. Details for structure 1 : a) The layer‐forming Na(1) and Na(3) cations are distributed over three distinctly separated planes, Na(1) occupies general positions and has a non‐octahedral O₅N environment, Na(3) resides on inversion centres that generate an octahedral O₆ coordination; b) one independent A^— is oriented vertically, the other parallel to the layer plane; c) the intercalated Na(2) ions occupy twofold rotation axes within a single plane and possess a non‐octahedral O₆ environment. Details for structure 2 : a) The layer‐forming K(1) and K(2) cations occupy twofold rotation axes within a unique plane and have chemically identically O₆N₂ coordination polyhedra approximating to hexagonal bipyramids; b) all A^— are oriented vertically to the layer plane; c) the intercalated sodium ions reside on pseudo‐inversion centres, have an octahedral O₆ environment and are distributed over two closely adjacent planes. Owing to the enhanced packing efficiency of the bimetal complex, the vertical layer repeat‐distance is reduced from 1140 pm for 1 to 720 pm for 2 . Each structure exhibits an infinite cation‐water chain that propagates in the direction of the layer stacking and contains the three independent cations.