Crystal Structure and Solid-State Packing of 4-Chloro-5H-1,2,3-dithiazol-5-one and 4-Chloro-5H-1,2,3-dithiazole-5-thione

Abstract

The crystal structure and solid-state packing of 4-chloro-5H-1,2,3-dithiazol-5-one and two polymorphs of 4-chloro-5H-1,2,3-dithiazole-5-thione were analyzed and compared to structural data of similar systems. These five-membered S,N-rich heterocycles are planar with considerable bond localization. All three structures demonstrate tight solid-state packing without voids which is attributed to a rich network of short intermolecular electrostatic contacts. These include Sδ+…Nδ−, Sδ+…Oδ−, Sδ+…Clδ− and Sδ+…Sδ− interactions that are well within the sum of their van der Waals radii (∑VDW). B3LYP, BLYP, M06, mPW1PW, PBE and MP2 were employed to calculate their intramolecular geometrical parameters, the Fukui condensed functions to probe their reactivity, the bond order, Bird Index and NICS(1) to establish their aromaticity.

Synthesis and crystal structure of 3-phenyl-1,4,2-dithiazole-5-thione

“…While the observed HÁ Á ÁS hydrogen bonding between the molecules is weak (AE van der Waals radii SÁ Á ÁH = 3.0 A ˚), they aid the orientation of the molecules within the out-of-plane chains. In contrast, the SÁ Á ÁS contact distance [3.575 (11) A ˚] may appear to be close to the accepted sum of the van der Waals radii (3.6 A ˚) but when the known anisotropy of sulfur contacts [in plane SÁ Á ÁS contact 3.20 A ˚and perpendicular SÁ Á ÁS contact 4.06 A ˚ (Constantinides et al, 2021)] are factored, it is revealed that the contact is a significant contributor to the supramolecular packing of the compound.…”

“…Comparison of the structure of the title compound with the structures of the isomeric ring systems 1,2,4-dithiazole-5thione (Stanford, 1963), 1,3,2-dithiazole-4-thione (Oakley et al, 1987), 1,2,3-dithiazole-5-thione (Constantinides et al, 2021) and the derivatives of 1,4,2-dithiazole (Oakley et al, 1993)…”