Supramolecular polymers of 4,5-bis(bromomethyl)-1,3-dithiole-2-thione-dihalogen adducts

Abstract

The title compound has been reacted with I-2, IBr and ICl to afford the charge-transfer adducts 4.2I(2), 4.IBr and 4.ICl.I-2, respectively. The products have been characterised by Raman and IR spectroscopy and X-ray crystallography. The adducts contain linear S...I-X (X=I, Br or Cl) units (174-178degrees) in which the S...I contacts range from 2.534-2.597 AAngstrom. In 4.2I(2) and 4.ICl.I-2, the materials contain additional 'free' diiodine units which are held within a matrix of intermolecular contacts, predominantly through non-covalent halogen halogen and sulfur-halogen interactions. Although the functional groups in the parent molecule (4) are inert at the supramolecular level, the bromomethyl groups in the adducts contribute strong interactions through Br...Br, Br...I, Br...S and Br...H close contacts. The structures of the complexes are polymeric in nature, providing interactions in two and three dimensions

Reactions Between Chalcogen Donors and Dihalogens/Interalogens: Typology of Products and Their Characterization by FT‐Raman Spectroscopy

“…Those obtained from molecules containing selenium and diiodine are less numerous [14, 25, 69–81], while few adducts of - and -donors with [57–60, 62–67, 81–83] and [60, 61, 67, 68, 83, 84] have been reported and structurally characterized in the literature. Three adducts of -donors have been characterized by X-ray diffraction analysis [65, 94], and no CT adducts of -donors are known with any dihalogen or interhalogen.…”

“…adducts with both - and -donors show one main peak in their FT-Raman spectra in the range 190–140 cm −1 [16, 59, 60, 62–67, 81] at a lower frequency with respect to solid [216 cm −1 , d (I−Br) = 2.521(4) Å] [98], and it is assignable to a stretching vibration of the E−I−Br three-body system having a major contribution from the ν (I−Br) vibration [63]. adducts (only four out of seven are both structurally and vibrationally characterized) [60, 67, 68] generally show in their FT-Raman spectra two main peaks: one in the range 240–180 cm −1 presumably due to the antisymmetric ( ν 3 ) stretching vibration of the E−I−Cl three body-system ( = , ), and the other at about 130 cm −1 due to the symmetric ( ν 1 ) stretching vibration (solid is characterized by a single peak at 283 cm −1 in its FT-Raman spectrum with a d (I−Cl) = 2.446(6) Å) [99]. Interestingly, by considering the Δ d (I−Y) parameter ( = , , ), a linear correlation appears also to exist between Δ d (I−Br) and ν (I−Br) for adducts, and between Δ d (I−Cl) and the ν (E−I−Cl) stretching mode corresponding to the ν antisym in symmetric three-body systems, for adducts (Figure 8).…”

The role of functional nitro and cyano groups in the self‐assembly of 1,3‐dithiole‐2‐thione–halogen adducts

“…In this "free" diiodine molecule, the bond length is 2.736(5)Å. Although the inclusion of additional halogen molecules in polyhalide chains has been seen in other systems [6,[8][9][10], the remaining structures in this work are simple 1:1 adducts. The adduct 6.1.5IBr is isostructural to 6.1.5I 2 , with the thiocarbonyl sulfur coordinating to the iodine atom of the interhalogen and the occupancy of the bromine/iodine atoms of the free molecule in a random distribution.…”

“…For instance, the incorporation of ferrocene in 1 results in an open shell species with magnetic properties, due to the oxidation of the metallocene during adduct formation [6]. Functionalities that interact with the halogen adduct include esters (compound 2) via hydrogen bonding [8,9] and methylene bromide side groups (in 3) which form halogen-halogen contacts [10]. These interactions participate in the self-assembly of the adducts to form highly ordered and polymeric supramolecular structures in the solid state.…”

Synthesis and structure of dithiocarbonimidates derived from aromatic heterocycles: Role of weak interactions in the preferred conformation

“…The sulfur interactions with electron donor atoms affect the conformation and secondary structure of biological molecules [8]. Interactions also act in molecular recognition and in the architecture of materials [9][10][11][12][13][14][15][16][17]. Specifically, sulfur-sulfur short contacts can be considered as acceptor donor pairs [18][19][20][21].…”