biostudies-literatureUran EThe Slovenian Research and Innovation AgencyEuropean Research CouncilInstitut \"Jožef Stefan\"7776-7784https://www.ebi.ac.uk/biostudies/studies/S-EPMC12659783biostudies-literatureUnknown27(48)The hydrogen-bonding ability of XeF<sub>2</sub> is an important factor influencing its chemical properties and reactivity, yet structurally characterised examples of hydrogen-bonded xenon fluorides remain rare. In this work, three salt cocrystals containing hydrogen-bonded xenon difluoride and hexafluoridoarsenate salts of protonated perfluoroamides-CF<sub>3</sub>C(OH)NH<sub>2</sub>[AsF<sub>6</sub>]·XeF<sub>2</sub>, C<sub>2</sub>F<sub>5</sub>C(OH)NH<sub>2</sub>[AsF<sub>6</sub>]·XeF<sub>2</sub>, and C<sub>3</sub>F<sub>7</sub>C(OH)NH<sub>2</sub>[AsF<sub>6</sub>]·XeF<sub>2</sub>-were synthesised and structurally characterised. Diverse hydrogen-bonding motifs were observed, and the first crystallographically characterised examples of N-H⋯FXeF hydrogen bonds are presented. In total, eleven new crystal structures are reported, including two perfluoroamides, three protonated and two hemiprotonated perfluoroamides, and one salt cocrystal containing an oxonium ion. The XeF<sub>2</sub>-containing cocrystals demonstrate that XeF<sub>2</sub> reliably functions as a hydrogen-bond acceptor and readily forms hydrogen-bonded cocrystals. These findings broaden the scope of noble-gas chemistry and highlight the potential of noble-gas fluorides for cocrystal formation.CrystEngCommHydrogen-bonded salt cocrystals of xenon difluoride and protonated perfluoroamides.PMC12659783950625J1-60022Director's FundLozinsek MUran EfalseHydrogen-bonded salt cocrystals of xenon difluoride and protonated perfluoroamides.The hydrogen-bonding ability of XeF<sub>2</sub> is an important factor influencing its chemical properties and reactivity, yet structurally characterised examples of hydrogen-bonded xenon fluorides remain rare. In this work, three salt cocrystals containing hydrogen-bonded xenon difluoride and hexafluoridoarsenate salts of protonated perfluoroamides-CF<sub>3</sub>C(OH)NH<sub>2</sub>[AsF<sub>6</sub>]·XeF<sub>2</sub>, C<sub>2</sub>F<sub>5</sub>C(OH)NH<sub>2</sub>[AsF<sub>6</sub>]·XeF<sub>2</sub>, and C<sub>3</sub>F<sub>7</sub>C(OH)NH<sub>2</sub>[AsF<sub>6</sub>]·XeF<sub>2</sub>-were synthesised and structurally characterised. Diverse hydrogen-bonding motifs were observed, and the first crystallographically characterised examples of N-H⋯FXeF hydrogen bonds are presented. In total, eleven new crystal structures are reported, including two perfluoroamides, three protonated and two hemiprotonated perfluoroamides, and one salt cocrystal containing an oxonium ion. The XeF<sub>2</sub>-containing cocrystals demonstrate that XeF<sub>2</sub> reliably functions as a hydrogen-bond acceptor and readily forms hydrogen-bonded cocrystals. These findings broaden the scope of noble-gas chemistry and highlight the potential of noble-gas fluorides for cocrystal formation.2025-01-01T00:00:00Z2025 Dec2026-06-06T15:31:53.75Z2026-06-01T03:10:59.792ZS-EPMC126597834132353310.1039/d5ce00956a