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However, their Li homologues have remained elusive. In this work, the highly condensed lithium (imido)nitridophosphates LiP<jats:sub>4<\/jats:sub>N<jats:sub>7<\/jats:sub> and Li<jats:sub>3\u2212<jats:italic>x<\/jats:italic><\/jats:sub>P<jats:sub>6<\/jats:sub>N<jats:sub>11\u2212<jats:italic>x<\/jats:italic><\/jats:sub>(NH)<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub> (<jats:italic>x<\/jats:italic>=1.66(3)) were synthesized from LiPN<jats:sub>2<\/jats:sub> and P<jats:sub>3<\/jats:sub>N<jats:sub>5<\/jats:sub> in the multianvil press at 10\u2005GPa. They constitute the first lithium nitridophosphates with 3D networks exhibiting a degree of condensation larger than 0.5 and high thermal stability. LiP<jats:sub>4<\/jats:sub>N<jats:sub>7<\/jats:sub> crystallizes in the orthorhombic space group <jats:italic>P<\/jats:italic>2<jats:sub>1<\/jats:sub>2<jats:sub>1<\/jats:sub>2<jats:sub>1<\/jats:sub> with <jats:italic>a<\/jats:italic>=4.5846(6)\u2005\u00c5, <jats:italic>b<\/jats:italic>=8.0094(11)\u2005\u00c5, and <jats:italic>c<\/jats:italic>=13.252(2)\u2005\u00c5 (<jats:italic>Z<\/jats:italic>=4). Li<jats:sub>3\u2212<jats:italic>x<\/jats:italic><\/jats:sub>P<jats:sub>6<\/jats:sub>N<jats:sub>11\u2212<jats:italic>x<\/jats:italic><\/jats:sub>(NH)<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub> crystallizes in the triclinic space group <jats:italic>P<\/jats:italic><jats:inline-graphic xmlns:xlink=\"http:\/\/www.w3.org\/1999\/xlink\" xlink:href=\"graphic\/chem202303251-math-0001.png\" xlink:title=\"urn:x-wiley:09476539:media:chem202303251:chem202303251-math-0001\"\/>\n with <jats:italic>Z<\/jats:italic>=2, <jats:italic>a<\/jats:italic>=4.6911(11)\u2005\u00c5, <jats:italic>b<\/jats:italic>=7.024(2)\u2005\u00c5, <jats:italic>c<\/jats:italic>=12.736(3)\u2005\u00c5, <jats:italic>\u03b1<\/jats:italic>=87.726(11), <jats:italic>\u03b2<\/jats:italic>=80.279(11), and <jats:italic>\u03b3<\/jats:italic>=70.551(12)\u00b0. Both compounds are stable against hydrolysis in air.<\/jats:p>","DOI":"10.1002\/chem.202303251","type":"journal-article","created":{"date-parts":[[2023,10,24]],"date-time":"2023-10-24T16:08:25Z","timestamp":1698163705000},"update-policy":"https:\/\/doi.org\/10.1002\/crossmark_policy","source":"Crossref","is-referenced-by-count":5,"title":["Please Mind the Gap: Highly Condensed P\u2013N Networks in LiP<sub>4<\/sub>N<sub>7<\/sub> and Li<sub>3\u2212<i>x<\/i><\/sub>P<sub>6<\/sub>N<sub>11\u2212<i>x<\/i><\/sub>(NH)<sub><i>x<\/i><\/sub>"],"prefix":"10.1002","volume":"30","author":[{"given":"Stefanie","family":"Schneider","sequence":"first","affiliation":[{"name":"Department of Chemistry University of Munich (LMU)  Butenandtstra\u00dfe 5\u201313 (D) 81377 Munich Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Sebastian","family":"Klenk","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Munich (LMU)  Butenandtstra\u00dfe 5\u201313 (D) 81377 Munich Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Simon D.","family":"Kloss","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Munich (LMU)  Butenandtstra\u00dfe 5\u201313 (D) 81377 Munich Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]},{"ORCID":"https:\/\/orcid.org\/0000-0003-4571-8035","authenticated-orcid":false,"given":"Wolfgang","family":"Schnick","sequence":"additional","affiliation":[{"name":"Department of Chemistry University of Munich (LMU)  Butenandtstra\u00dfe 5\u201313 (D) 81377 Munich Germany"}],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"311","published-online":{"date-parts":[[2023,11,20]]},"reference":[{"key":"e_1_2_9_1_1","doi-asserted-by":"publisher","DOI":"10.1007\/978-3-642-50076-3"},{"key":"e_1_2_9_2_1","doi-asserted-by":"publisher","DOI":"10.1016\/0022-4596(90)90070-E"},{"key":"e_1_2_9_3_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201700979"},{"key":"e_1_2_9_4_1","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.19976230112"},{"key":"e_1_2_9_5_1","doi-asserted-by":"publisher","DOI":"10.1002\/anie.199108301"},{"key":"e_1_2_9_5_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19911030723"},{"key":"e_1_2_9_6_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201704305"},{"key":"e_1_2_9_7_1","doi-asserted-by":"publisher","DOI":"10.1002\/chem.201704975"},{"key":"e_1_2_9_8_1","doi-asserted-by":"publisher","DOI":"10.1021\/acs.inorgchem.6b01611"},{"key":"e_1_2_9_9_1","doi-asserted-by":"publisher","DOI":"10.1002\/zaac.19976230923"},{"key":"e_1_2_9_10_1","first-page":"19561","volume":"7","author":"Eckerlin P.","year":"1960","journal-title":"Angew. 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