S1 Supporting Information Craig Weinberger, [a] Rachel Hines, [a] Matthias Zeller [b] and Sergiy V. Rosokha* [a] Continuum of Covalent to Intermolecular Bonding in the Halogen-Bonded Complexes of 1,4- Diazabicyclo[2.2.2]octane with Bromine-Containing Electrophiles a Department of Chemistry, Ball State University, Muncie, IN, 47306, USA b Department of Chemistry, Purdue University, West Lafayette, Indiana 47907, USA E-mail: svrosokha@bsu.edu Table of Contents Pages A) UV-Vis and NMR measurements and their treatments Calculation of equilibria constants and spectral characteristics S2 Results of the UV-Vis measurements of the formation of [CHI3, A - ] complexes and their initial treatment (Figures S1-S6) S3-S8 Job’s plot (Figure S7) S9 B) Single crystal growth and X-ray crystallographic analysis Details of the preparation of single crystals of halogen-bonded complexes and crystallographic measurements S10 Crystallographic parameters and the details of the structure refinements (Table S1) S12 Halogen-bonded networks (Figure S8) S13 C) Quantum-mechanical computations Details of the computations S14 Examples of the structures of calculated complexes (Figure S9) S14 Energies of the XB complexes (Table S2) S15 Geometric characteristics of the calculated XB (Table S3) S16 Spectral characteristics of the calculated XB (Table S4) S17 Correlations between experimental and calculated halogen bond length and energies (Figure S10) S18 Atomic coordinates of the calculated XB complexes S19 Electronic Supplementary Material (ESI) for ChemComm. This journal is © The Royal Society of Chemistry 2018