Two new limiting series of ternary compounds with ordered defects have been evidenced, which crystallize with hexagonal symmetry, space group P6m2. The first one (direct series) shows one metal vacancy and corresponds to the chemical formula &R n1 2 T n3 2 À3 X n2 2 . The compounds a-UCr 6 P 4 (n = 0) and Zr 4 Co 13 Si 9 (n = 1) are the first members of the series. X-ray single crystal determination and/or electron microprobe analysis confirm the ternary phosphides Ce 9 Ni 25 P 13 and Ce 16 Ni 36 P 22 to be the following members. The second family (reverse series) with chemical formula R& n1 2 T n3 2 À3 X n2 2 comprises the ternaries a-UCr 6 P 4 (in fact member n = 0 in both series) and UMo 13 P 9 (n = 1), the structure of which has been determined on a single crystal. The limiting structures to which the two series converge have been found to be YbPtP (direct) and WC (reverse). The structural relationships between the direct and reverse series have been discussed in terms of metal vacancies and coordination polyhedra. Moreover, a general crystal chemical rule has been established that permits prediction of the different members for the two series and their structural definition in terms of lattice parameters, atomic coordinates and theoretical X-ray diffraction patterns. Finally, this rule permits to give for each member the number of metal vacancies as well as the distribution of the metalloid polyhedra occupied by the metal atoms (trigonal prisms, pyramids, tetrahedra, triangles).beide Serien konvergieren, wurden YbPtP (direkt) und WC (invers) gefunden. Die strukturelle Verwandtschaft zwischen direkten und inversen Reihen wurde auf der Basis von Metall-Leerstellen und der Koordinationspolyhedra diskutiert. Weiters wurde eine kristallchemische Regel aufgestellt, die eine Vorhersage der verschiedenen Vertreter fu È r die beiden Serien und ihre Strukturbestimmung in Bezug auf Gitterparameter, Atomkoordinaten und theoretische Ro È ntgendiffraktogramme ermo È glicht. Schluûendlich erlaubt diese Regel fu È r alle Vertreter beider Reihe die Anzahl der Metall-Leerstellen sowie die Verteilung der Metalloid-Polyhedra, welche von Metallatomen besetzt werden (trigonale Prismen, Pyramiden, Tetrahedra und Dreiecke) anzugeben.
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