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A piperidine and a pyrrolidine\u2010based nitroxide radical are compared and show clear differences in the preferred directionality of H\u2010bond formation. We demonstrate that these scenarios are best represented in<jats:sup>17<\/jats:sup>O hf spectra, where in\u2010plane coordination over<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/anie202213700-math-0001.png\" xlink:title=\"urn:x-wiley:14337851:media:anie202213700:anie202213700-math-0001\"\/>\u2010type H\u2010bonding leads to little spin density transfer on the water oxygen and small hf couplings, whereas<jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/anie202213700-math-0002.png\" xlink:title=\"urn:x-wiley:14337851:media:anie202213700:anie202213700-math-0002\"\/>\u2010type perpendicular coordination generates much larger hf couplings. Quantitative analysis of the spectra based on MD simulations and DFT predicted hf parameters is consistent with a distribution of close solvating water molecules, in which directionality is influenced by subtle steric effects of the ring and the methyl group substituents.<\/jats:p>","DOI":"10.1002\/anie.202213700","type":"journal-article","created":{"date-parts":[[2022,11,18]],"date-time":"2022-11-18T18:12:15Z","timestamp":1668795135000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":14,"title":["<sup>17<\/sup>O Hyperfine Spectroscopy Reveals Hydration Structure of Nitroxide Radicals in Aqueous Solutions"],"prefix":"10.1002","volume":"62","author":[{"ORCID":"https:\/\/orcid.org\/0000-0001-7262-5497","authenticated-orcid":false,"given":"Fabian","family":"Hecker","sequence":"first","affiliation":[{"name":"Research Group EPR spectroscopy Max Planck Institute for Multidisciplinary Sciences Am Fassberg 11 37077 G\u00f6ttingen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-3123-0514","authenticated-orcid":false,"given":"Lisa","family":"Fries","sequence":"additional","affiliation":[{"name":"Research Group EPR spectroscopy Max Planck Institute for Multidisciplinary Sciences Am Fassberg 11 37077 G\u00f6ttingen Germany"},{"name":"Current address: Center for Biostructural Imaging of Neurodegeneration Medical Center G\u00f6ttingen Von-Siebold-Stra\u00dfe 3a 37075 G\u00f6ttingen Germany"},{"name":"NMR Signal Enhancement Group Max Planck Institute for Multidisciplinary Sciences Am Fassberg 11 37077 G\u00f6ttingen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Markus","family":"Hiller","sequence":"additional","affiliation":[{"name":"Research Group EPR spectroscopy Max Planck Institute for Multidisciplinary Sciences Am Fassberg 11 37077 G\u00f6ttingen Germany"},{"name":"Current address: Isotope Technologies Dresden Rossendorfer Ring 42 01328 Dresden Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-8128-8031","authenticated-orcid":false,"given":"Mario","family":"Chiesa","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Torino Via Giuria 9 10125 Torino Italy"}],"role":[{"vocabulary":"crossref","role":"author"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-6784-7845","authenticated-orcid":false,"given":"Marina","family":"Bennati","sequence":"additional","affiliation":[{"name":"Research Group EPR spectroscopy Max Planck Institute for Multidisciplinary Sciences Am Fassberg 11 37077 G\u00f6ttingen Germany"},{"name":"Department of Chemistry Georg August University G\u00f6ttingen Tammanstrasse 2 37077 G\u00f6ttingen Germany"}],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2022,12,15]]},"reference":[{"key":"e_1_2_3_1_1","unstructured":"\u00a0"},{"key":"e_1_2_3_2_2","volume-title":"Nitroxide Spin Labels","author":"Kocherginsky N.","year":"1995"},{"key":"e_1_2_3_3_2","doi-asserted-by":"publisher","DOI":"10.1002\/9780470034590.emrstm1513"},{"key":"e_1_2_3_4_1","unstructured":"\u00a0"},{"key":"e_1_2_3_5_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja061284b"},{"key":"e_1_2_3_6_2","doi-asserted-by":"publisher","DOI":"10.1038\/nchem.2723"},{"key":"e_1_2_3_7_1","doi-asserted-by":"publisher","DOI":"10.1016\/j.pnmrs.2013.06.001"},{"key":"e_1_2_3_8_1","doi-asserted-by":"publisher","DOI":"10.1039\/c3gc41459k"},{"key":"e_1_2_3_9_1","doi-asserted-by":"publisher","DOI":"10.1021\/ma00122a058"},{"key":"e_1_2_3_10_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.202115908"},{"key":"e_1_2_3_10_2","doi-asserted-by":"crossref","first-page":"e202115908","DOI":"10.1002\/ange.202115908","volume":"134","year":"2022","journal-title":"Angew. 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