The Stannides Nd 3 Pd 5 Sn 5 , Gd 3 Pd 4.96(1) Sn 5 , and GdPdSn

The stannides Nd 3 Pd 5 Sn 5 and Gd 3 Pd 4.96(1) Sn 5 were obtained by arc‐melting of the elements. Nd 3 Pd 5 Sn 5 and Gd 3 Pd 4.96(1) Sn 5 crystallize with the monoclinic Sm 3 Pd 4.95 Sn 5 type structure, space group C 2/ m . Both structures were refined from single crystal diffractometer data: a = 1729.5(4), b = 454.51(8), c = 1428.2(3) pm, β = 99.71(2)°, wR 2 = 0.0689, 2220 F 2 values, 82 variables for Nd 3 Pd 5 Sn 5 and a = 1712.2(2), b = 450.36(9) c = 1412.0(3) pm, β = 99.804(2)°, wR 2 = 0.0526, 1834 F 2 values, 83 variables for Gd 3 Pd 4.96(1) Sn 5 . The Pd2 site of the gadolinium compound showed site occupancy of only 95.8(7) %. The palladium and tin atoms in these monoclinic stannides build up complex three‐dimensional [Pd 5 Sn 5 ] δ – polyanionic networks, which leave cavities for the three crystallographically independent rare earth sites: RE 1@Pd 6 Sn 8 , RE 2@Pd 7 Sn 8 , and RE 3@Pd 6 Sn 9 . The networks are stabilized by Pd–Sn, Pd–Pd as well as Sn–Sn bonding. The rare earth atoms bind to the networks via shorter RE –Pd contacts. The Gd 3 Pd 4.96(1) Sn 5 crystal showed an adherent second domain, which consisted of GdPdSn: TiNiSi type, Pnma , a = 725.6(3), b = 461.3(3), c = 790.6(3) pm, wR 2 = 0.0973, 431 F 2 values, 20 variables.