{"status":"ok","message-type":"work","message-version":"1.0.0","message":{"indexed":{"date-parts":[[2025,12,4]],"date-time":"2025-12-04T15:07:42Z","timestamp":1764860862529,"version":"3.46.0"},"reference-count":50,"publisher":"International Union of Crystallography (IUCr)","issue":"12","license":[{"start":{"date-parts":[[2025,11,10]],"date-time":"2025-11-10T00:00:00Z","timestamp":1762732800000},"content-version":"vor","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/legalcode"},{"start":{"date-parts":[[2025,11,10]],"date-time":"2025-11-10T00:00:00Z","timestamp":1762732800000},"content-version":"tdm","delay-in-days":0,"URL":"https:\/\/creativecommons.org\/licenses\/by\/4.0\/legalcode"}],"content-domain":{"domain":["iucr.org","wiley.com","iucrj.org"],"crossmark-restriction":true},"short-container-title":["Acta Crystallogr C Struct Chem","Acta Crystallogr C","Acta Crystallogr C Cryst Struct Commun","Acta Cryst C","Acta Cryst C Struct Chem","Acta Cryst Sect C","Acta Cryst Sect C Struct Chem","Acta Crystallogr Sect C","Acta Crystallogr Sect C Struct Chem","Acta Crystallogr Sect C Cryst Struct Commun"],"accepted":{"date-parts":[[2025,10,29]]},"published-print":{"date-parts":[[2025,12,1]]},"abstract":"<jats:p>\n                    The molecular structures of two novel cobalt aminodiphosphine (PNP) complexes (\n                    <jats:bold>1<\/jats:bold>\n                    and\n                    <jats:bold>2<\/jats:bold>\n                    ) are reported, namely, bis[bis(diphenylphosphanyl)(pentyl)amine-\u03ba\n                    <jats:sup>2<\/jats:sup>\n                    <jats:italic>P<\/jats:italic>\n                    ,\n                    <jats:italic>P<\/jats:italic>\n                    \u2032]chloridocobalt(III) di-\u03bc-chlorido-bis[dichloridocobalt(II)], [CoCl(C\n                    <jats:sub>29<\/jats:sub>\n                    H\n                    <jats:sub>31<\/jats:sub>\n                    NP\n                    <jats:sub>2<\/jats:sub>\n                    )\n                    <jats:sub>2<\/jats:sub>\n                    ][Co\n                    <jats:sub>2<\/jats:sub>\n                    Cl\n                    <jats:sub>6<\/jats:sub>\n                    ], and bis[bis(diphenylphosphanyl)(propan-2-yl)amine-\u03ba\n                    <jats:sup>2<\/jats:sup>\n                    <jats:italic>P<\/jats:italic>\n                    ,\n                    <jats:italic>P<\/jats:italic>\n                    \u2032]chloridocobalt(III) di-\u03bc-chlorido-bis[dichloridocobalt(II)], [CoCl(C\n                    <jats:sub>27<\/jats:sub>\n                    H\n                    <jats:sub>27<\/jats:sub>\n                    NP\n                    <jats:sub>2<\/jats:sub>\n                    )\n                    <jats:sub>2<\/jats:sub>\n                    ][Co\n                    <jats:sub>2<\/jats:sub>\n                    Cl\n                    <jats:sub>6<\/jats:sub>\n                    ], featuring variation in the N-atom substituent,\n                    <jats:italic>i.e.<\/jats:italic>\n                    <jats:italic>n<\/jats:italic>\n                    -pentyl in complex\n                    <jats:bold>1<\/jats:bold>\n                    and isopropyl in complex\n                    <jats:bold>2<\/jats:bold>\n                    . The asymmetric unit of complex\n                    <jats:bold>1<\/jats:bold>\n                    contains a five-coordinated cationic [CoCl{\u03ba\n                    <jats:sup>2<\/jats:sup>\n                    -\n                    <jats:italic>P<\/jats:italic>\n                    ,\n                    <jats:italic>P<\/jats:italic>\n                    -(\n                    <jats:italic>N<\/jats:italic>\n                    )-C\n                    <jats:sub>5<\/jats:sub>\n                    H\n                    <jats:sub>11<\/jats:sub>\n                    }\n                    <jats:sub>2<\/jats:sub>\n                    ]\n                    <jats:sup>2+<\/jats:sup>\n                    species and a [Co\n                    <jats:sub>2<\/jats:sub>\n                    (\u03bc\n                    <jats:sub>2<\/jats:sub>\n                    -Cl)\n                    <jats:sub>2<\/jats:sub>\n                    Cl\n                    <jats:sub>4<\/jats:sub>\n                    ]\n                    <jats:sup>2\u2212<\/jats:sup>\n                    anion, while complex\n                    <jats:bold>2<\/jats:bold>\n                    includes a five-coordinated cation [CoCl{\u03ba\n                    <jats:sup>2<\/jats:sup>\n                    -\n                    <jats:italic>P<\/jats:italic>\n                    ,\n                    <jats:italic>P<\/jats:italic>\n                    -(\n                    <jats:italic>N<\/jats:italic>\n                    )-C\n                    <jats:sub>3<\/jats:sub>\n                    H\n                    <jats:sub>7<\/jats:sub>\n                    }\n                    <jats:sub>2<\/jats:sub>\n                    ], half a [Co\n                    <jats:sub>2<\/jats:sub>\n                    (\u03bc\n                    <jats:sub>2<\/jats:sub>\n                    -Cl)\n                    <jats:sub>2<\/jats:sub>\n                    Cl\n                    <jats:sub>4<\/jats:sub>\n                    ]\n                    <jats:sup>2\u2212<\/jats:sup>\n                    anion, and disordered diethyl ether and dichloromethane solvent molecules. The impact of ligand-induced strain, particularly due to the small bite angles of the PNP aminodiphosphine ligands, was examined in the context of geometric constraints and their influence on stability and reactivity. A Cambridge Structural Database (CSD) survey, along with a noncovalent interaction (NCI) analysis of the analogous [TMCl\n                    <jats:sub>\n                      <jats:italic>n<\/jats:italic>\n                    <\/jats:sub>\n                    (PNP)\n                    <jats:sub>2<\/jats:sub>\n                    ] (where TM\u00a0= transition metal and\n                    <jats:italic>n<\/jats:italic>\n                    \u00a0= 1 or 2) core, revealed an inverse correlation between P\u2014TM\u2014P bite angles and N...TM contact distances. This correlation is attributed to the influence of the van der Waals radius of the metal: smaller metals allow wider bite angles and stronger N...TM contacts, whereas larger metals favour narrower bite angles and longer N...TM distances. NCI analysis indicated significant steric repulsion at the TM...N contacts, reflecting strain imposed by ligand geometry. A comparison of sign(\u03bb\n                    <jats:sub>2<\/jats:sub>\n                    )\u03c1 eigenvalues suggests that Mo\u2014P bonds exhibit weaker attractive interactions relative to Co\u2014P and Ru\u2014P bonds, with Cr\u2014P bonds being the weakest. These findings provide pointers to structural and electronic factors governing coordination in PNP-ligated transition-metal complexes, offering rational design and catalytic and material applications.\n                  <\/jats:p>","DOI":"10.1107\/s2053229625009519","type":"journal-article","created":{"date-parts":[[2025,11,10]],"date-time":"2025-11-10T17:03:36Z","timestamp":1762794216000},"page":"694-701","update-policy":"https:\/\/doi.org\/10.1107\/cm_01","source":"Crossref","is-referenced-by-count":0,"title":["Structural insights into transition-metal\u2013aminodiphosphine (PNP) complexes bearing [\n                    <i>M<\/i>\n                    Cl\n                    <sub>\n                      <i>n<\/i>\n                    <\/sub>\n                    (PNP)\n                    <sub>2<\/sub>\n                    ] (\n                    <i>M<\/i>\n                    \u00a0= Co, Ru, Cr or Mo;\n                    <i>n<\/i>\n                    \u00a0= 1 or 2) cores in the solid state"],"prefix":"10.1107","volume":"81","author":[{"ORCID":"https:\/\/orcid.org\/0000-0003-1968-381X","authenticated-orcid":true,"given":"Sizwe J.","family":"Zamisa","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0001-9287-5960","authenticated-orcid":true,"given":"Adesola A.","family":"Adeleke","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Dunesha","family":"Naicker","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0002-1329-0815","authenticated-orcid":true,"given":"Holger B.","family":"Friedrich","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Bernard","family":"Omondi","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"329","published-online":{"date-parts":[[2025,11,10]]},"reference":[{"key":"ef3070_bb1","doi-asserted-by":"crossref","first-page":"1349","DOI":"10.1039\/DT9840001349","author":"Addison","year":"1984","journal-title":"J. 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