{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,9,19]],"date-time":"2025-09-19T07:37:36Z","timestamp":1758267456759,"version":"3.33.0"},"reference-count":31,"publisher":"International Union of Crystallography (IUCr)","issue":"11","license":[{"start":{"date-parts":[[2016,10,4]],"date-time":"2016-10-04T00:00:00Z","timestamp":1475539200000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/2.0\/uk\/legalcode"},{"start":{"date-parts":[[2016,10,4]],"date-time":"2016-10-04T00:00:00Z","timestamp":1475539200000},"content-version":"tdm","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/2.0\/uk\/legalcode"}],"content-domain":{"domain":["iucr.org","wiley.com","iucrj.org"],"crossmark-restriction":true},"short-container-title":["Acta Crystallogr E Cryst Commun","Acta Cryst E","Acta Cryst Sect E","Acta Crystallogr E","Acta Crystallogr Sect E","Acta Cryst E Cryst Commun","Acta Cryst Sect E Cryst Commun"],"accepted":{"date-parts":[[2016,9,29]]},"published-print":{"date-parts":[[2016,11,1]]},"abstract":"<jats:p>Crystals of bis(tetrabutylammonium) di-\u03bc<jats:sub>3<\/jats:sub>-chlorido-tris(\u03bc<jats:sub>2<\/jats:sub>-4-iodopyrazolato-\u03ba<jats:sup>2<\/jats:sup>\n                  <jats:italic>N<\/jats:italic>:<jats:italic>N<\/jats:italic>\u2032)tris[chloridocuprate(II)] 1,4-dioxane hemisolvate, (C<jats:sub>16<\/jats:sub>H<jats:sub>36<\/jats:sub>N)<jats:sub>2<\/jats:sub>[Cu<jats:sub>3<\/jats:sub>(C<jats:sub>3<\/jats:sub>H<jats:sub>2<\/jats:sub>IN<jats:sub>2<\/jats:sub>)<jats:sub>3<\/jats:sub>Cl<jats:sub>5<\/jats:sub>]\u00b70.5C<jats:sub>4<\/jats:sub>H<jats:sub>8<\/jats:sub>O or (Bu<jats:sub>4<\/jats:sub>N)<jats:sub>2<\/jats:sub>[Cu<jats:sup>II<\/jats:sup>\n                  <jats:sub>3<\/jats:sub>(<jats:italic>\u03bc<\/jats:italic>\n                  <jats:sub>3<\/jats:sub>-Cl)<jats:sub>2<\/jats:sub>(<jats:italic>\u03bc<\/jats:italic>-4-I-pz)<jats:sub>3<\/jats:sub>Cl<jats:sub>3<\/jats:sub>]\u00b70.5C<jats:sub>4<\/jats:sub>H<jats:sub>8<\/jats:sub>O, were obtained by evaporating a solution of (Bu<jats:sub>4<\/jats:sub>N)<jats:sub>2<\/jats:sub>[{Cu<jats:sup>II<\/jats:sup>(<jats:italic>\u03bc<\/jats:italic>-OH)(<jats:italic>\u03bc<\/jats:italic>-4-I-pz)}<jats:sub>\n                     <jats:italic>n<\/jats:italic>\n                  <\/jats:sub>CO<jats:sub>3<\/jats:sub>] (<jats:italic>n<\/jats:italic> = 27\u201331) nanojars in chloroform\/1,4-dioxane. The decomposition of chloroform in the presence of oxygen and moisture provides HCl, which leads to the breakdown of nanojars to the title trinuclear copper(II) pyrazolate complex, and possibly Cu<jats:sup>II<\/jats:sup> ions and free 4-iodopyrazole. Cu<jats:sup>II<\/jats:sup> ions, in turn, act as catalyst for the accelerated decomposition of chloroform, ultimately leading to the complete breakdown of nanojars. The crystal structure presented here provides the first structural description of a trinuclear copper(II) pyrazolate complex with iodine-substituted pyrazoles. In contrast to related trinuclear complexes based on differently substituted 4-<jats:italic>R<\/jats:italic>-pyrazoles (<jats:italic>R<\/jats:italic> = H, Cl, Br, Me), the [Cu<jats:sub>3<\/jats:sub>(<jats:italic>\u03bc<\/jats:italic>-4-I-pz)<jats:sub>3<\/jats:sub>Cl<jats:sub>3<\/jats:sub>] core in the title complex is nearly planar. This difference is likely a result of the presence of the iodine substituent, which provides a unique, novel feature in copper pyrazolate chemistry. Thus, the iodine atoms form halogen bonds with the terminal chlorido ligands of the surrounding complexes [mean length of I...Cl contacts = 3.48\u2005(1)\u2005\u00c5], leading to an extended two-dimensional, halogen-bonded network along (-110). The cavities within this framework are filled by centrosymmetric 1,4-dioxane solvent molecules, which create further bridges <jats:italic>via<\/jats:italic> C\u2014H...Cl hydrogen bonds with terminal chlorido ligands of the trinuclear complex not involved in halogen bonding.<\/jats:p>","DOI":"10.1107\/s205698901601536x","type":"journal-article","created":{"date-parts":[[2016,10,4]],"date-time":"2016-10-04T08:22:12Z","timestamp":1475569332000},"page":"1517-1520","update-policy":"https:\/\/doi.org\/10.1107\/cm_01","source":"Crossref","is-referenced-by-count":7,"title":["Halogen-bonded network of trinuclear copper(II) 4-iodopyrazolate complexes formed by mutual breakdown of chloroform and nanojars"],"prefix":"10.1107","volume":"72","author":[{"given":"Stuart A.","family":"Surmann","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Gellert","family":"Mezei","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"329","published-online":{"date-parts":[[2016,10,4]]},"reference":[{"key":"gk2666_bb1","doi-asserted-by":"crossref","first-page":"8327","DOI":"10.1039\/C6DT00847J","volume":"45","author":"Ahmed","year":"2016","journal-title":"Dalton Trans."},{"key":"gk2666_bb2","doi-asserted-by":"crossref","unstructured":"Ahmed, B. 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