title: Synthesis and Crystal Structure of Zr(2)Te. Distinctions in Bonding to Isotypic Sc(2)Te and the Relationship to the Structures of Congeneric Hf(2)Te and Zr(2)Se.
abstract: Zr(2)Te is accessible by high-temperature synthesis. The structure of the zirconium-rich telluride was determined by means of powder X-ray diffraction to be orthorhombic, Pnma (No. 62), Z = 12, Pearson symbol oP36, a = 1995.0(2) pm, b = 382.36(2) pm, c = 1065.63(9) pm. Pairwise interpenetrating columns of trans-face-shared, centered Zr(9) cuboids, reminiscent of the bcc high-temperature form of zirconium can be recognized as the topologically characteristic structural feature. Tellurium atoms capping the remaining square faces complete the motif of a [Zr(8)Te(4)] double string running parallel [010]. The tellurium atoms are 7-, 8- and 9-fold coordinated by zirconium. The coordination figures represent mono-, bi- and tricapped distorted trigonal prisms, with zirconium atoms capping the square faces of the prisms. Extended Hückel calculations revealed distinctions in bonding in Zr(2)Te and the isotypic Sc(2)Te. According to Mulliken overlap populations, the heteronuclear interactions are similar in both tellurides. However, the lower valence electron concentration available for M-M bonding in Sc(2)Te is reflected in a considerable restriction of the attractive homonuclear interactions to one-dimensional metal cores, whereas in Zr(2)Te M-M bonding regions extend in space. The structure of Zr(2)Te is contrasted with two other types of bcc fragment structures adopted by the congeneric Hf(2)Te and Zr(2)Se. We show that the structural diversity observed for various dimetal chalcogenides is controlled by an intimate interplay of electronic and geometric factors.
authors.affiliation: Department of Chemistry and Materials Science Centre, Philipps University, D-35032 Marburg, Germany.
authors.forename: Gissur
authors.initials: G
authors.lastname: Örlygsson
authors.forename: Bernd
authors.initials: B
authors.lastname: Harbrecht