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The Metal-rich Phosphide Ce4

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The Metal-rich Phosphide Ce

4

Ir

13.55

P

9

Ulrike Pfannenschmidt, Ute Ch. Rodewald, and Rainer P¨ottgen

Institut f¨ur Anorganische und Analytische Chemie, Universit¨at M¨unster, Corrensstraße 30, 48149 M¨unster, Germany

Reprint requests to R. P¨ottgen. E-mail: pottgen@uni-muenster.de Z. Naturforsch.2011,66b,7 – 13; received October 1, 2010

Needle-shaped crystals of the metal-rich phosphide Ce4Ir13.55P9 were synthesized from the el- ements in a lead flux (starting composition 1 : 2 : 2 : 60) at 1370 K followed by slow cooling.

Ce4Ir13.55P9crystallizes with a new orthorhombic structure type:Pnma,a= 1269.1(2),b= 399.1(1), c= 3349.9(7) pm,wR2 = 0.0722, 2025F2values and 139 variables. Two of the 14 crystallographic iridium sites show small defects. All phosphorus atoms have slightly distorted tricapped trigonal pris- matic metal coordination by cerium and iridium. The iridium and phosphorus atoms build up a three- dimensional [Ir13.55P9]δ− polyanion in which the cerium atoms fill distorted hexagonal cavities.

Within the polyanion the phosphide anions are isolated, and one additionally observes a broad range of Ir–Ir bonding (Ir–Ir distances 278 – 298 pm). From a geometrical point of view the Ce4Ir13.55P9

structure can be considered as an intergrowth structure of distorted ThCr2Si2- and SrPtSb-related slabs.

Key words:Phosphide, Cerium, Crystal Chemistry

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