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Z. Naturforsch. 2014,
69b, 1124 – 1130
doi:10.5560/ZNB.2014-4115
Zr4CuSb7 – A PbFCl-related Polyantimonide, and Structure Relations of Zirconium-Transition Metal Polyantimonides
Fachgebiet Synthese und Charakterisierung innovativer Materialien, Deptartment Chemie, Technische Universität München, Lichtenbergstraße 4, 85747 Garching, Germany
Reprint requests to Prof. Dr. Tom Nilges. Fax: +49 89 289 13110. E-mail:
tom.nilges@lrz.tum.de
Received May 29, 2014 / published online December 19, 2014
Dedicated to Professor Hubert Schmidbaur on the occasion of his 80th birthday
Single crystals of tetrazirconium copper heptaantimonide were obtained by arc-melting and annealing from the elements in ideal ratios including a 10 % excess of Sb. The excess of Sb is needed to compensate for the evaporation loss during arc-melting synthesis. Zr4CuSb7 crystallizes tetragonally, space group P4bm (no. 100) as a racemic twin. It adopts a unique structure that can be regarded as a composite of a PbClF unit and a layered, partially copper-substituted polyantimonide substructure. Zr4CuSb7 represents a filling and substitution variant of the Hf5Sb9 structure type. The copper atoms fill voids and partially replace antimony atoms in the 4.82 Sb net of the Hf5Sb9
polyantimonide substructure to form a distorted 44 net in Zr4CuSb7. Structure relations to known zirconium-transition metal polyantimonides are given, and new structures are predicted based on these relations.
Key words: Transition Metal Polyphosphide, Sb–Sb Bonding, Structure Chemistry of Polyantimonides