doi:10.1002/ejic.202500315engPérez-Bitrián, AlbertoJoven-Sancho, DanielBaya, MiguelMartín, AntonioOrduna, JesúsMenjón, BabilDifferentiating between F and OH Ligands in Homologous Gold(III) Complexes beyond X‐Ray CrystallographyART-2025-146109The homologous fluoride and hydroxide complexes of gold(III) [PPh4][(CF3)3AuX] [X = F (1), OH (2)] have been structurally characterized by single-crystal X-ray diffraction methods. Both of them crystallize in the P21/n space group, yet they are not isomorphous. Despite the intrinsic difficulty to distinguish between F− and OH− by X-ray diffraction, the ability of the OH ligand in complex 2 to establish intramolecular OH…F hydrogen bonding with one of the CF3 groups in cis position enables a clear differentiation from the fluoride complex 1. Given the tendency of late-transition metal fluorides to undergo hydrolysis, much caution should be taken when ascribing the identity of a fluoride ligand by X-ray diffraction methods, especially where unusual geometries are implied.2025http://zaguan.unizar.es/record/16394810.1002/ejic.202500315http://zaguan.unizar.es/record/163948oai:zaguan.unizar.es:163948info:eu-repo/grantAgreement/ES/DGA/E17-23Rinfo:eu-repo/grantAgreement/ES/MICIU/PID2021-122869NB-I00info:eu-repo/grantAgreement/ES/MICIU/PID2024-155563NB-I00European Journal of Inorganic Chemistry 28, 34 (2025), e202500315 [10 pp.]by-nc-ndhttps://creativecommons.org/licenses/by-nc-nd/4.0/deed.esinfo:eu-repo/semantics/openAccess