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The lithium rhodium stannide LiRh 3 Sn 5  was synthesized from the elements in a sealed tantalum tube and investigated via X-ray powder and single crystal diffraction: Pbcm, a = 538.9(1), b = 976.6(3), c = 1278.5(3) pm, wR2 = 0.0383, 1454 F 2  values, and 44 variables. Refinement of the occupancy parameters revealed a lithium content of 92(6)%. LiRh 3 Sn 5  crystallizes with a new structure type. The structure is built up from a complex three-dimensional [Rh 3 Sn 5 ] network, in which the lithium atoms fill channels in the b direction. The [Rh 3 Sn 5 ] network is governed by Rh-Rh (274 - 295 pm), Rh-Sn (262 - 287 pm), and Sn-Sn (289 - 376 pm) interactions. The lithium atoms have CN 13 (4 Rh+9 Sn). Electronic band structure calculations and the COHP bond analysis reveal strong Rh−Sn bonds and also significant Rh−Rh bonding within the Rh 3 Sn 5  network, which is additionally stabilized by weak but frequent Sn−Sn interactions.

The Stannide LiRh 3 Sn 5 – Synthesis, Structure, and Chemical Bonding