Crystal structures of isotypic poly[bis-(benz-imid-azolium) [tetra-μ-iodido-stannate(II)]] and poly[bis-(5,6-di-fluoro-benzimidazolium) [tetra-μ-iodido-stannate(II)]].

The isostructural title compounds, {(C7H7N2)2[SnI4]} n , (1), and {(C7H5F2N2)2[SnI4]} n , (2), show a layered perovskite-type structure composed of anionic {SnI4} n sheets parallel to (100), which are decorated on both sides with templating benzimidazolium or 5,6-di-fluoro-benzimidazolium cations, respectively. These planar organic heterocycles mainly form N-H⋯I hydrogen bonds to the terminal I atoms of the corner-sharing [SnI6] octa-hedra (point group symmetry 2) from the inorganic layer, but not to the bridging ones. This is in contrast to most of the reported structures of related compounds where ammonium cations are involved. Here hydrogen bonding to both types of iodine atoms and thereby a distortion of the inorganic layers to various extents is observed. For (1) and (2), all Sn-I-Sn angles are linear and no out-of-plane distortions of the inorganic layers occur, a fact of relevance in view of the material properties. The arrangement of the aromatic cations is mainly determined through the direction of the N-H⋯I hydrogen bonds. The coherence between organic bilayers along [100] is mainly achieved through van der Waals inter-actions.