The staple role of hydrogen and halogen bonds in crystalline (E)-8-((2,3-diiodo-4-(quinolin-8-ylthio)but-2-en-1-yl)thio)quinolin-1-ium triiodide

Abstract

The staple role of hydrogen and halogen bonds in crystalline (E)-8-((2,3-diiodo-4-(quinolin-8-ylthio)but-2-en-1-yl)thio)quinolin-1-ium triiodide Abstract The crystal structure of (E)-8-((2,3-diiodo-4-(quinolin-8-ylthio)but-2-en-1-yl)thio)quinolin-1-ium triiodide, determined at 100 K in the space group C2/c, contains the bridge hydrogen bond [NÁÁÁHÁÁÁN] ? linking two neighboring quinolinium fragments; the distance NÁÁÁN is 2.6927(15) Å . The experimental difference Fourier maps at 293 and 100 K lead to a conclusion about the dynamic nature of the H atom disorder. Calculated vibrational modes obtained for the same compound in the space groups C2/c and Cc are in agreement with the experimental Raman spectrum in the low-frequency region; together, they are consistent with a previous supposition about the dynamic nature of the H atom disorder. We have found that the cation-anion interactions are realized through the charge-assisted iodine-iodine halogen bond.

Electronic criterion for categorizing the chalcogen and halogen bonds: sulfur–iodine interactions in crystals

“…Careful attention is paid to the particular case of noncovalent interactions between chalcogen and iodine atoms in the following investigations (Arman et al, 2010(Arman et al, , 2012Bartashevich et al, 2016;Konidaris et al, 2018;Jay et al, 2001;Kobra et al, 2018;Liu et al, 2009;Resnati & Pennington, 2018). Careful attention is paid to the particular case of noncovalent interactions between chalcogen and iodine atoms in the following investigations (Arman et al, 2010(Arman et al, , 2012Bartashevich et al, 2016;Konidaris et al, 2018;Jay et al, 2001;Kobra et al, 2018;Liu et al, 2009;Resnati & Pennington, 2018).…”

Raman spectroscopy and theoretic study of hyperpolarizability effect in diiodobutenyl‐bis‐thioquinolinium triiodide at low temperature

“…According to X‐ray diffraction data, there are no significant changes in atomic positions of the C, N, S, I atoms at room temperature and at 100 K. Nevertheless, Raman spectra demonstrate several changes in the temperature range from 153 K down to 113 K (Fig. a).…”

“…Ruby‐red single crystals of diiodobutenyl‐ bis ‐thioquinolinium triiodide ( 1 ) were obtained according to experimental procedure described previously …”

“…Heterocyclic N,‐S‐containing quinoline polyiodides are prominent candidates for the usage in various fields of novel material design, due to their great structural diversity and potentialities for functionalization. Recently, the structural features of diiodobutenyl‐ bis ‐thioquinolinium triiodide have been studied by X‐ray diffraction and first‐principles calculations . The key problem of the previous research was the determination of the position of bridge hydrogen atom, resulting in uncertainty of total symmetry: C2/c [NHN] + versus Cc [N–H…N] + .…”

“…Recently, the structural features of diiodobutenyl‐ bis ‐thioquinolinium triiodide have been studied by X‐ray diffraction and first‐principles calculations . The key problem of the previous research was the determination of the position of bridge hydrogen atom, resulting in uncertainty of total symmetry: C2/c [NHN] + versus Cc [N–H…N] + . Recent study has drawn attention to the role of polar distortions in similar hydrogen‐bonded frameworks and its role in determination of ferroelectric properties.…”