Interestingly, in both SM33 and SM36 the difference in local density in the first solvation shell around the amine N in neat 1-octanol and water-saturated 1-octanol is insignificant. We find that in neat 1-octanol, in both cases, the local density in the first solvation shell is larger than the ring S and sulfone S. The secondary amine N-H is the only solute hydrogen bond donating site, and the secondary amine N-H is known to be a moderate hydrogen bond donor and acceptor . Possibly in neat 1-octanol the secondary amine is already "saturated" with hydrogen bonds, such that the local density is not impacted by the addition of water. For the case of SM36, the (ring) sulfoxide S=O is a moderate hydrogen bond acceptor . But as compared to the secondary amine, it is more sterically free, and can better accommodate hydrogen bonding with the solvent. We see this in the large halo of 1-octanol O around the sulfoxide in the SDF in figure of the Supporting Information.