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The intermetallic compound K<jats:sub>5\u2212<jats:italic>x<\/jats:italic><\/jats:sub>Co<jats:sub>1\u2212<jats:italic>x<\/jats:italic><\/jats:sub>Sn<jats:sub>9<\/jats:sub> was obtained by the reaction of a preformed Co\uf8ffSn alloy with potassium and tin at high temperatures. The diamagnetic saltlike ternary phase contains discrete [Co@Sn<jats:sub>9<\/jats:sub>]<jats:sup>5\u2212<\/jats:sup> clusters that are separated by K<jats:sup>+<\/jats:sup> ions. The intermetallic compound K<jats:sub>5\u2212<jats:italic>x<\/jats:italic><\/jats:sub>Co<jats:sub>1\u2212<jats:italic>x<\/jats:italic><\/jats:sub>Sn<jats:sub>9<\/jats:sub> readily and incongruently dissolves in ethylenediamine and in the presence of 4,7,13,16,21,24\u2010hexaoxa\u20101,10\u2010diazabicyclo[8.8.8]hexacosane (2.2.2\u2010crypt), thereby leading to the formation of crystalline [K([2.2.2]crypt)]<jats:sub>5<\/jats:sub>[Co<jats:sub>2<\/jats:sub>Sn<jats:sub>17<\/jats:sub>]. The novel polyanion [Co<jats:sub>2<\/jats:sub>Sn<jats:sub>17<\/jats:sub>]<jats:sup>5\u2212<\/jats:sup> contains two Co\u2010filled Sn<jats:sub>9<\/jats:sub> clusters that share one vertex. Both compounds were characterized by single\u2010crystal X\u2010ray structure analysis. The diamagnetism of K<jats:sub>5\u2212<jats:italic>x<\/jats:italic><\/jats:sub>Co<jats:sub>1\u2212<jats:italic>x<\/jats:italic><\/jats:sub>Sn<jats:sub>9<\/jats:sub> and the paramagnetism of [K([2.2.2]crypt)]<jats:sub>5<\/jats:sub>[Co<jats:sub>2<\/jats:sub>Sn<jats:sub>17<\/jats:sub>] have been confirmed by superconducting quantum interference device (SQUID) and EPR measurements, respectively. Quantum chemical calculations reveal an endohedral Co<jats:sup>1\u2212<\/jats:sup> atom in an [Sn<jats:sub>9<\/jats:sub>]<jats:sup>4\u2212<\/jats:sup> <jats:italic>nido<\/jats:italic> cluster for [Co@Sn<jats:sub>9<\/jats:sub>]<jats:sup>5\u2212<\/jats:sup> and confirm the stability of the paramagnetic [Co<jats:sub>2<\/jats:sub>Sn<jats:sub>17<\/jats:sub>]<jats:sup>5\u2212<\/jats:sup> unit.<\/jats:p>","DOI":"10.1002\/chem.201201786","type":"journal-article","created":{"date-parts":[[2012,8,9]],"date-time":"2012-08-09T08:35:49Z","timestamp":1344501349000},"page":"12000-12007","source":"Crossref","is-referenced-by-count":49,"title":["The Neat Ternary Solid K<sub>5\u2212<i>x<\/i><\/sub>Co<sub>1\u2212<i>x<\/i><\/sub>Sn<sub>9<\/sub> with Endohedral [Co@Sn<sub>9<\/sub>]<sup>5\u2212<\/sup> Cluster Units: A Precursor for Soluble Intermetalloid [Co<sub>2<\/sub>@Sn<sub>17<\/sub>]<sup>5\u2212<\/sup> Clusters"],"prefix":"10.1002","volume":"18","author":[{"given":"Viktor","family":"Hlukhyy","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Haiyan","family":"He","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Laura\u2010Alice","family":"Jantke","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Thomas F.","family":"F\u00e4ssler","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2012,8,9]]},"reference":[{"key":"e_1_2_7_1_2","unstructured":"\u00a0"},{"key":"e_1_2_7_2_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19961080204"},{"key":"e_1_2_7_2_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199601291"},{"key":"e_1_2_7_3_2","doi-asserted-by":"crossref","first-page":"3682","DOI":"10.1002\/1521-3757(20021004)114:19<3682::AID-ANGE3682>3.0.CO;2-6","volume":"114","author":"Schnepf A.","year":"2002","journal-title":"Angew. 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