Abstract: | Polysulfonylamines. CLIV. Crystal Structures of Metal Di(methanesulfonyl)amides. 7. A Three‐Dimensional Coordination Polymer Built up from Layers and Pillars: Crystal Structure of Ba(CH3SO2)2N]2·2H2O The barium compound BaA2·2H2O, derived from HA = di(methanesulfonyl)amine, has been characterized by single crystal X‐ray diffraction at —95 °C (monoclinic, space group P21/n, Z = 4). Despite numerous metal‐ligand bonds, the independent anions A— and A′— retain the pseudo‐C2 symmetric conformation that commonly occurs in organic onium salts BH+A—. The large cation attains ninefold coordination via interactions with one (O, N)‐chelating A—, three κ1O‐bonding A—, two κ1O‐bonding A′— and two monodentate water molecules; if a distinctly longer barium‐water distance is included, the coordination number may alternatively be viewed as 9 + 1 and one water molecule regarded as an asymmetrically μ2‐bridging ligand. In contrast to the previously reported layer structures of SrA2 and PbA2, the present crystal displays a three‐dimensional coordination assembly consisting of layers formed by the cations, the water molecules and the pentadentate A— ligands, and of interlayer pillars provided by the bidentate A′— ligands; however, the Ba2+/A— substructure turns out to be topologically and crystallographically congruent with the corresponding M2+/A— substructures in SrA2 and PbA2. The crystal cohesion of the barium complex is reinforced by four O(W)—H···O=S hydrogen bonds and several non‐classical C—H···O=S hydrogen bonds. |