The Predicted Structures of the New Pnictides HfMQ in Contrast to ZrMQ (M = Ti, V; Q = P, As)

The new pnictides HfTiP, HfTiAs and HfVAs have been prepared through arc‐melting. These arsenides form the predicted structures with (distorted) TiAs 4 and VAs 4 tetrahedra, while the structures of both Zr analogs (ZrTiAs and ZrVAs) are comprised of TiAs 4 and VAs 4 square planes, respectively. These differences stem from significant differences in the metal atom substructures. On the other hand, HfTiP and ZrTiP are isostructural. These variations were predicted by utilizing a structure map for metal‐rich pnictides and chalcogenides M 2 Q (M = valence‐electron poor transition metal, Q = pnicogen or chalcogen) presented in the year 2000. The HfMQ structure is stabilized by strong Hf−Q, M−Q and M−M bonds, and to a minor extent by Hf−Hf and Hf−M bonding interactions. All three new Hf 1−δ M 1+δ Q phases exhibit significant phase ranges. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)