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The crystal structure has been studied using single-crystal X-ray experimental data. The pseudo-hexagonal phase NaZnAl(PO<jats:sub>4<\/jats:sub>)<jats:sub>2<\/jats:sub>crystallizes in the monoclinic space group<jats:italic>P<\/jats:italic>2<jats:sub>1<\/jats:sub>\/<jats:italic>c<\/jats:italic>. Its unique crystal structure is based on a three-dimensional (3D) framework built by Zn-, Al- and P-centred tetrahedra sharing vertices. Channels parallel to the [101] and [\\overline{1}01] directions are limited by six- and eight-membered windows, and incorporate Na atoms. The new compound is discussed as a member of the morphotropic series<jats:italic>AMM<\/jats:italic>\u2032PO<jats:sub>4<\/jats:sub>, where<jats:italic>A<\/jats:italic>= Na, K, Rb or NH<jats:sub>4<\/jats:sub>,<jats:italic>M<\/jats:italic>\u00a0= Cu, Ni, Co, Fe, Zn or Mg and<jats:italic>M<\/jats:italic>\u2032 = Fe, Al or Ga. The title compound is the first Na representative within the series and is characterized by a 3D architecture of tetrahedra populated in an ordered manner by Zn<jats:sup>2+<\/jats:sup>, Al<jats:sup>3+<\/jats:sup>and P<jats:sup>5+<\/jats:sup>ions.<\/jats:p>","DOI":"10.1107\/s2053229619004327","type":"journal-article","created":{"date-parts":[[2019,4,8]],"date-time":"2019-04-08T15:32:37Z","timestamp":1554737557000},"page":"514-522","update-policy":"https:\/\/doi.org\/10.1107\/cm_01","source":"Crossref","is-referenced-by-count":7,"title":["The rich crystal chemistry of the<i>AMM<\/i>\u2032(PO<sub>4<\/sub>)<sub>2<\/sub>morphotropic series: NaZnAl(PO<sub>4<\/sub>)<sub>2<\/sub>, the first Na representative with a new structure type"],"prefix":"10.1107","volume":"75","author":[{"ORCID":"https:\/\/orcid.org\/0000-0002-7495-8460","authenticated-orcid":true,"given":"Olga","family":"Yakubovich","sequence":"first","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Galina","family":"Kiriukhina","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Anatoliy","family":"Volkov","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]},{"given":"Olga","family":"Dimitrova","sequence":"additional","affiliation":[],"role":[{"role":"author","vocabulary":"crossref"}]}],"member":"329","published-online":{"date-parts":[[2019,4,8]]},"reference":[{"key":"fn3303_bb1","unstructured":"Agilent (2012). 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