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Bifurcated XBs, albeit rare, are unambiguously established in crystalline solids but do not correspond to an energetically favorable arrangement at the molecular level. Here the dynamic behavior of such a system, jointly described by experiment and theory, reconciles both aspects: Experiment shows that the cocrystal of 1,4\u2010diiodobenzene and 1,4\u2010dinitrobenzene with a symmetric bifurcated XB undergoes a rarely observed reversible crystal\u2010to\u2010crystal transition at 130\u00a0K. The resulting low\u2010 temperature phase features an asymmetric bifurcated XB, a first step toward a more linear arrangement. Theoretical calculations based on revised van der Waals density functional theory and diffraction experiments conducted at high resolution agree remarkably well in their interpretation of transition temperature and relevance of interaction types. The XB is fluxional and entropy\u2010favored in the symmetric high\u2010 temperature phase and locks into an asymmetric geometry with slightly more favorable Gibbs free energy at low temperature; the energy differences involved are extremely small. Theoretically derived and experimentally observed electron densities agree that the perceived directional interactions are weak rather than decisive synthons. Stacking of alternating diiodobenzene and dinitrobenzene molecules represents the most relevant contact.<\/jats:p>","DOI":"10.1002\/chem.202502514","type":"journal-article","created":{"date-parts":[[2025,11,7]],"date-time":"2025-11-07T08:41:56Z","timestamp":1762504916000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":0,"title":["Fluxional Halogen Bonds Versus Interlayer Stacking \u2013 Theory Meets Experiment"],"prefix":"10.1002","volume":"31","author":[{"given":"Cai Yue","family":"Gao","sequence":"first","affiliation":[{"name":"Institute of Molecular Science Shanxi University  Taiyuan 030006 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Annika","family":"Schmidt","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry TU Dortmund University  44227 Dortmund Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Ruimin","family":"Wang","sequence":"additional","affiliation":[{"name":"Institute of Molecular Science Shanxi University  Taiyuan 030006 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Carsten","family":"Strohmann","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry TU Dortmund University  44227 Dortmund Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-2623-0061","authenticated-orcid":false,"given":"Ulli","family":"Englert","sequence":"additional","affiliation":[{"name":"Institute of Inorganic Chemistry RWTH Aachen University  52056 Aachen Germany"},{"name":"Institute of Environmental and Chemical Engineering Jiangsu University of Science and Technology  Zhenjiang 212003 China"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Si\u2010Dian","family":"Li","sequence":"additional","affiliation":[{"name":"Institute of Molecular Science Shanxi University  Taiyuan 030006 China"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2025,11,7]]},"reference":[{"key":"e_1_2_8_1_1","doi-asserted-by":"publisher","DOI":"10.1107\/S2052520616003954"},{"key":"e_1_2_8_2_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199523111"},{"volume-title":"An Introduction to Hydrogen Bonding","year":"1997","author":"Jeffrey G. 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