An investigation of halogen bonding as a structure-directing interaction in dithiadiazolyl radicals

Published as part of a Crystal Growth and Design virtual special issue on Crystalline Molecular Materials: From Structure to Function.The preparation and characterization of the halo-functionalized dithiadiazolyl radicals p-XC6F4CNSSN (X = Br (1) or I (2)) are described. Compound 1 is trimorphic. The previously reported phase 1α (Z′ = 1) comprises monomeric radicals, whereas 1β comprises a mixture of one cis-oid π*−π* dimer and one monomer (Z′ = 3), and 1γ exhibits a single cis-oid dimer (Z′ = 2) in the asymmetric unit. We have only been able to isolate a single polymorph of 2, isomorphous with 1α. Both the bromo and iodo groups in 1 and 2 promote sigma-hole type interactions of the type C–X···N (X = Br, I), reflecting the increasing strength of this interaction for the heavier halo-derivatives. An analysis of the intermolecular forces is made using dispersion corrected density functional theory (DFT) (UM06-2X-D3/LACV3P*) and compared to a unified pair potential model (UNI) embodied in the crystallographic software Mercury. While there is a correlation between DFT and UNI force-field models, there are some discrepancies, although both reveal that a number of intermolecular contacts beyond the sum of the van der Waals radii are significant (>5 kJ mol–1). A natural bond order analysis of the intermolecular interactions reveals lone pair donation from the heterocyclic N atom to C–X or S–S σ* orbitals contributes to these intermolecular interactions with relative energies in the order C–I > SN-II > C–Br > SN-III. The magnetism of 2 reveals a broad maximum in χ around 20 K indicative of short-range antiferromagnetic interactions. These are supported by DFT calculations that reveal a set of three significant exchange interactions which propagate in two dimensions.We would like to acknowledge the NSERC DG program for financial support (J.M.R.) and C.F.I./O.R.F. for an infrastructure grant. M.A.N. would like to thank the NSERC for a CGS-M scholarship. J.C. acknowledges support from Grant PGC-2018−099024-B100. Additional support from Diputacion General de Aragon (DGA-M4) is also acknowledged. J.C and A.A. would like to acknowledge the use of Servicio General de Apoyo a la Investigacion-SAI, Universidad de Zaragoza.Peer reviewe