Description:
<jats:title>Abstract</jats:title><jats:p>Tetrahedra‐based nitridophosphates show a rich structural chemistry, which can be further extended by incorporating cations in higher coordinated positions, for example, in octahedral voids or by substituting the nitrogen atoms in the network with other anions. Following this approach, SrAl<jats:sub>5</jats:sub>P<jats:sub>4</jats:sub>N<jats:sub>10</jats:sub>O<jats:sub>2</jats:sub>F<jats:sub>3</jats:sub> was synthesized at high‐temperature and high‐pressure conditions using a multianvil press (1400 °C, 5 GPa) starting from Sr(N<jats:sub>3</jats:sub>)<jats:sub>2</jats:sub>, c‐PON, P<jats:sub>3</jats:sub>N<jats:sub>5</jats:sub>, AlN, and NH<jats:sub>4</jats:sub>F. SrAl<jats:sub>5</jats:sub>P<jats:sub>4</jats:sub>N<jats:sub>10</jats:sub>O<jats:sub>2</jats:sub>F<jats:sub>3</jats:sub> crystallizes in space group <jats:inline-graphic xmlns:xlink="http://www.w3.org/1999/xlink" xlink:href="graphic/chem202301960-math-0001.png" xlink:title="urn:x-wiley:09476539:media:chem202301960:chem202301960-math-0001" />
with <jats:italic>a</jats:italic>=11.1685(2) and <jats:italic>c</jats:italic>=7.84850(10) Å. Atomic‐resolution EDX mapping with scanning transmission electron microscopy (STEM) indicates atom assignments, which are further corroborated by bond‐valence sum (BVS) calculations. Ten Al<jats:sup>3+</jats:sup>‐centered octahedra form a highly condensed tetra‐face‐capped octahedra‐based unit that is a novel structure motif in network compounds. A network of vertex‐sharing PN<jats:sub>4</jats:sub> tetrahedra and chains of face‐sharing Sr<jats:sup>2+</jats:sup>‐centered cuboctahedra complement the structure. Eu<jats:sup>2+</jats:sup>‐doped SrAl<jats:sub>5</jats:sub>P<jats:sub>4</jats:sub>N<jats:sub>10</jats:sub>O<jats:sub>2</jats:sub>F<jats:sub>3</jats:sub> shows blue emission (<jats:italic>λ</jats:italic><jats:sub>em=</jats:sub>469 nm, fwhm=98 nm; 4504 cm<jats:sup>−1</jats:sup>) when irradiated with UV light.</jats:p>