The calculated structures of TEPO*SO3 and pyridine*SO3 have tetrahedral structures, as expected. The N-S bond length is 1.839 Å and the sum of the O-S-O bond angles (SOSO) is 348.3. The S-O bond lengths are 1.441, 1.442, and 1.474, respectively. The longest S-O bond is also interacting with a zirconium on the surface. These metrics are very similar to crystallographically characterized pyridine*SO3 (SOSO = 348.2; dN-S = 1.828(5) Å, dS=O = 1.416(5), 1.421(6), and 1.429(5) Å, respectively). These bond length and angle patterns are also observed in the TEPO*SO3 adduct, but pyramidalization is more significant (SOSO = 332.85), which is reflective of the stronger adduct formed between TEPO and the pyrosulfate compared to pyridine.