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The stannides LnRu 4 Sn 6  (Ln = La, Pr, Nd, Sm, Gd) were prepared by reaction of the elements in an arc-melting furnace and subsequent annealing at 1120 K. The praseodymium, the neodymium, and the samarium stannide were obtained for the first time. The LnRu 4 Sn 6  stannides were investigated by X-ray diffraction both on powders and single crystals. They adopt the YRu 4 Sn 6  type structure which was refined from single crystal X-ray data for the samarium and the gadolinium compound: I4̄2m, a = 686.1 (1), c = 977.7(2) pm, wR2 = 0.0649, 483 F 2  values for SmRu 4 Sn 6 , and a = 685.2(1), c = 977.6(3) pm, wR2 = 0.0629, 554 F 2  values for GdRu 4 Sn 6  with 19 variables for each refinement. The striking structural motif of these stannides are distorted RuSn 6  octahedra with Ru-Sn distances ranging from 257 to 278 pm. Four of such octahedra are condensed via common edges and faces forming [Ru 4 Sn 6 ] units which are packed in a tetragonal body-centered arrangement. The rare-earth atoms fill the voids between the [Ru 4 Sn 6 ] units. Based on an extended Hückel calculation, strong bonding interactions were found for the Ru-Sn and the various Sn-Sn contacts.

Condensed [Ru 4 Sn 6 ] Units in the Stannides LnRu 4 Sn 6 (Ln = La, Pr, Nd, Sm, Gd) - Synthesis, Structure, and Chemical Bonding