I₅^–polymers with a layered arrangement: synthesis, spectroscopy, and structure of a new polyiodide salt in the nicotine/HI/I₂system

Abstract

The reaction of S-nicotine with hydroiodic acid in the presence of iodine gave the new polyiodidecontaining salt nicotine-1,1′-diium bis(triiodide)-diiodine (1/1) (C 10 H 16 N 2 ) [I 3 ] 2 ·I 2 (1). The title compound has been characterised by spectroscopic methods (Raman and IR) and single-crystal X-ray diffraction. The asymmetric unit of the title structure consists of one dication, two triiodide anions, and one iodine molecule, all located in general positions in the non-centrosymmetric space group P1. One of the two crystallographically independent triiodide anions and the doubly protonated nicotinium dication form hydrogen-bonded chains along b, which are arranged parallel to each other in the ½bc plane. The second crystallographically independent triiodide anion and the iodine molecule form an I 5 -moiety, which is end-on connected to two symmetry-related anions resulting in polyiode zig-zag chains along the [0 1 1̅ ] direction. These polyiodide chains are stacked parallel to each other in the 0bc plane. The Raman spectrum of the title compound shows characteristic lines in the 50-200 cm -1 range, which are in excellent agreement with the findings derived from the crystal structure.

Hydrogen bonding versus packing effects in the crystal structure of 3-((1R,2S)-1-methylpyrrolidin-1-ium-2-yl)pyridin-1-ium tetraiodidozincate(II), C10H16I4ZnN2

“…As reported and summarized by one of us [7] structural data are available for (a) metal complexes, which contain neutral nicotine ligands; (b) a small number of co-crystals containing neutral nicotine as one of the components; (c) some examples for pyrrolidinylmonoprotonated nicotinium salts; and (d) mono-protonated nicotinium as a cationic ligand. As a result of the database survey specified above, only a limited number of examples of salt structures containing doubly protonated nicotinium cations have been reported so far [7][8][9][10][11][12]. This contribution is part of our continuing interest in synthesis, characterization and understanding of hydrogen-bonding schemes of salts of natural products [7,[11][12][13][14].…”

A cyclic I10 2− anion in the layered crystal structure of theophyllinium pentaiodide, C7H9I5N4O2

“…Apart from possible applications there is still an academic interest in the synthesis of new, tailored polyiodides using cationic templates whose lengths and shapes may influence the topology of the polyiodide anions [18][19][20]. We have shown that semi-flexible cations [21][22][23] and heterocyclic cations like pyridinium derivatives [24,25] or naturally occurring base like nicotine [26] or caffeine [27] are excellent tectons for the synthesis of polyiodide containing salts. Many structures with the formal I5 − anion are known [9,19,26], but to the best of our knowledge, only one dimeric cyclic (I5 − ) 2 anion has been reported [28] until now.…”

“…We have shown that semi-flexible cations [21][22][23] and heterocyclic cations like pyridinium derivatives [24,25] or naturally occurring base like nicotine [26] or caffeine [27] are excellent tectons for the synthesis of polyiodide containing salts. Many structures with the formal I5 − anion are known [9,19,26], but to the best of our knowledge, only one dimeric cyclic (I5 − ) 2 anion has been reported [28] until now. From the reaction of theophylline (systematic name: 1,3dimethyl-3,7-dihydro-1H-purine-2,6-dione) with hydroiodic acid in the presence of excess iodine, black, shiny, block crystals of the title compound were obtained.…”

The crystal structure of 3-((1R,2S)-1-methylpyrrolidin-1-ium-2-yl)pyridin-1-ium tetrachloridocobaltate(II) monohydrate, C10H18Cl4CoN2O

“…Further surveys of crystal structures containing such mono and diprotonated nicotinium cations were recently carried out [6]. To the best of our knowledge, only four examples of salts containing doubly protonated nicotinium cations have been reported so far [6][7][8][9].…”

“…Further surveys of crystal structures containing such mono and diprotonated nicotinium cations were recently carried out [6]. To the best of our knowledge, only four examples of salts containing doubly protonated nicotinium cations have been reported so far [6][7][8][9]. This contribution is part of our continuing interest in synthesis, characterisation and understanding of hydrogen bonding schemes of tetrahalogenido-and hexahalogenidometallates [10] on the one hand and pyridinium salts on the other hand [11].…”