Crystallographic identification of a novel 2,4,5-tri(N-methyl-4-pyridinium)-1,3-thiazole with a complex network of polyiodide/iodine counter ions and co-crystallized cyclododecasulfur (S12)
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Date
2021
Authors
Shotonwa, Ibukun O.
Boeré, René T.
Journal Title
Journal ISSN
Volume Title
Publisher
Atlanta Publishing House
Abstract
The crystals of an unprecedented 2,4,5-tri(N-methylpyridinium)-1,3-thiazole are
monoclinic and belong to the space group P21/c as determined by single-crystal XRD. Crystal
data for C21H21I13N4S5.98: monoclinic, a = 7.5627(5) Å, b = 30.6764(19) Å, c = 20.8848(15) Å,
β = 91.632(6)°, V = 4843.2(6) Å3, Z = 4, T = 100.01(10) K, μ(Cu Kα) = 67.840 mm-1, Dcalc =
2.977 g/cm3, 17906 reflections measured (7.152° ≤ 2Θ ≤ 162.94°), 17906 unique (Rsigma =
0.0607) which were used in all calculations. The final R1 was 0.1366 (I > 2σ(I)) and wR2 was
0.3926 (all data). The crystal lattice contains 2,4,5-tri(N-methylpyridinium)-1,3-thiazole,
molecular iodine and triiodide counterions which interact with one another to
coordinatively form polyiodides, as well as a surprising co-crystallized neutral molecule of
cyclododecasulfur (S12). Close monitoring of the synthetic procedure reveals chemical
condensation and decomposition of the thioamide reagent to be the impetus for the
formation of individual components of the crystal lattice. Analysis of the XRD, including a
Hirshfeld surface analysis, shows that (a) the crystal lattice has a number of stabilizing
Coulombic short contacts such as I∙∙∙I, I∙∙∙S, I∙∙∙C, and C∙∙∙S and non-classical C-H∙∙∙I and C-H∙∙∙S
hydrogen bond interactions (b) the iodine/iodide network are major determinants in the
stability of its crystal lattice despite the reduced occupancies of sulfur and (c) the Hirshfeld
analysis in comparison with the conventional Mercury visualization program was able to
simplify, identify and quantify complex atom-atom interactions such as H∙∙∙H and N∙∙∙I in its
crystal lattice. Herein, it is reported, for the first time, the formation of co-crystallized,
neutral cyclododecasulfur (S12) from thioamide as the sulfur source. S12 displays a consistent
geometry and comparable average S-S distances, S-S-S angles and torsion angles with
previously reported crystal structures of S12. The complex network facilitated by the
formation of polyiodides via the interaction of symmetric and asymmetric triiodides and
iodine has resulted in quite strong interactions that are less than the sums of the van der
Waals radii of two connected atoms as well as an array of fascinating geometrical alignments
such as T-shape, trigonal pyramidal and L-shape.
Description
Open access article. Creative Commons Attribution-NonCommercial 4.0 International License (CC BY-NC 4.0) applies
Keywords
1,3-Thiazole , Sulfur heterocycles , Crystal engineering , Single crystal structure
Citation
Shotonwa, I. O., & Boere, R. T. (2021). Crystallographic identification of a novel 2,4,5-tri(N-methyl-4-pyridinium)-1,3-thiazole with a complex network of polyiodide/iodine counter ions and co-crystallized cyclododecasulfur (S12). European Journal of Chemistry, 12(2), 179-186. https://doi.org/10.5155/eurjchem.12.2.179-186.2108