Polysulfonylamines. CLX. Crystal structures of metal di(methanesulfonyl)amides. 10. The three-dimensional coordination polymers M[(CH3SO2)(2)N], where M is potassium, rubidium, cesium (isotypic structures for M=K, Rb

摘要

Low-temperature X-ray crystal structures are reported for KA (monoclinic, space group P2(1)/c, Z' = 1), RbA (isotypic and isostructural with KA), and CsA (monoclinic, P2(1), Z' = 1), where A(-) denotes the anion obtained by deprotonation of the strong nitrogen acid (MeSO2)(2)NH. In KA and RbA, the anion is distorted into a rare C, conformation, whereas the standard C-2 conformation is retained in the cesium complex. The structures consist of three-dimensional coordination networks, in which each cation adopts an irregular (O6N)-heptacoordination by forming close contacts to one (O,N)-chelating, one (O,O)-chelating and three kappa(1)O-bonding ligands; however, the coordination number for Cs+ is effectively increased to 8 by a very short Cs...Cs contact distance of 422.5 pm. The crystal packings of the isotypic compounds KA and RbA display lamellar layer substructures that involve six independent ligand-metal bonds and comprise an internal cation lamella and peripheral regions built up from anion monolayers; the 3D framework is completed by one independent M-O bond cross-linking the layer substructures. In contrast, CsA features anion monolayers that intercalate planar zigzag chains of cations (Cs...Cs alternatingly 422.5 and 487.5 pm, Cs...Cs...Cs 135.7degrees), whereby each chain is surrounded and coordinated by four anion stacks and each anion stack connects two cation chains. All structures exhibit close C-H...A interanion contacts consistent with weak hydrogen bonding. [References: 20]