Synthesis, Structure and Spectroscopy of a New Polyiodide in the α,ω-Diazaniumalkane Iodide/Iodine System

Abstract

The reaction of 1,4-diaminobutane with hydroiodic acid in the presence of iodine yields the title compound 1,4-diazaniumbutane tetraiodide, C 4 H 14 N 2 I 4 (1). The title compound has been structurally characterized by crystallographic and spectroscopic methods (Raman and IR). 1 is built up by centrosymmetric 1,4-diazaniumbutane cations in all-trans conformation and linear I 4 2− anions. Both, cations and anions are located on centers of inversion (2/m) in the monoclinic space group C2/m. The hydrogen bonds between the azanium groups and the terminal iodine atoms of the I 4 2− anions lead to a three-dimensional framework. The structural parameters of the tetraiodide anion, derived from X-ray crystallographic data are in excellent agreement with the results from Raman spectroscopy. The Raman and IR data for the analogous α,ω-diazaniumalkane tetraiodide salts (H 3 N-(CH 2 ) 6 -NH 3 )I 4 (2) and (H 3 N-(CH 2 ) 7 -NH 3 )I 4 (3) are reported, and the structures of 1, 2 and 3 are compared.

(3-Ammonio-2,2-dimethyl-propyl)carbamate Dihydrate

“…These results may be very valuable for future studies on the stability and mechanism of chemical carbon dioxide absorption in the context of recycling carbon dioxide. This contribution forms part of our longstanding interest in salts of diamines in general [45][46][47] and those of dmpn salts in detail [48].…”

Hydrogen bonds and van der Waals forces as tools for the construction of a herringbone pattern in the crystal structure of hexane-1,6-diaminium hexane-1,6-diyl bis(hydrogen phosphonate)

“…At this point it is not our aim to review all these structures, but we think it is worth highlighting some important classes of compounds and applications. The structures and properties of many simple salts of H16AH, like halides (van Blerk & Kruger, 2008), acetates (Paul & Kubicki, 2009) and salts with more complex inorganic anions such as hexafluoridosilcate (Ouasri et al, 2014), tetraiodide (Reiss & van Megen, 2012) or dihydrogen arsenate (Wilkinson & Harrison, 2007) have been extensively studied. Moreover, the H16AH dication is well known for its use in crystal engineering of hydrogen-bonded solids which contain unstable species (Frank & Reiss, 1997), in supramolecular chemistry (Assaf & Nau, 2015), as a tecton for the construction of layered materials (Bujoli-Doeuff et al, 2012), or as a cationic template for novel complex systems (Holtby et al, 2007).…”

Crystal structure of 3-aminium-pyridin-1-ium bis(triiodide) dihydrate, C5H12I6N2O2

“…Especially the monoprotonated cations are known to inactivate K + channels reversibly [8]. Polyiodides are defined as extended ionic structures that fulfill the general formula I (2m+n) n-(n =1-4, m =integer).They are formally built from I -,I 3 -and I 2 units and show astrong tendency to concatenate to extended motifs by halogen halogen interactions [9, 10].Moreover there is afocus on diaminium and pyridinium iodides and corresponding polyiodides, as they have asignificant influence on the redox chemistry in dye-sensitized solar cells [11, 12].In the recent past, several groups have synthesized new polyiodides using stick-shaped cations whose lengths andshapes fit with the structures of the polyiodide anions [13][14][15][16].I np articular, the semi-flexible a,w-diazaniumalkane dicationsh aves uccessfully been used for the synthesis of aseries of new polyiodide salts [4,[17][18][19][20]. Nitrogen based heterocyclic cations are also known to template the synthesis of new polyiodides [21][22][23].This contribution is part of our ongoing interest in the structural chemistry of iodide and polyiodide containing compounds.…”

“…Found, %: C, 6.83; H, 1.28; N, 3.19; I, 85.02. For details on theelemental analytical methods used, see general procedures giveninthe literature [3,4]. For the quantitative analysis of iodine alternatively aluminium was used as the reducing agent.…”