The metal-rich compounds [PdBi₆][(Bi,Sn) _1-δBr_5-δ] with δ₁ = 2/13, δ₁ = 5/26, or δ₂= δ'₂ = 1In were synthesized from Bi₂Pd, BiBr₃, and Sn at 300 °C. The crystal structures contain, intermetallic rods ¹ _∞[Pd@Bi_2/1Bi_8/2]^2,5+embedded in salt-like matrices, which, consist of groups of bromido-bismuthate(III)- stannate(H) octahedra [(Bi,Sn)_nBI_4n+2]^m- (n = 2, 3) and isolated Br^- ions. Metrical incompatibilities of the two subsystems in the crystalline metal-salt hybrid result in non-stoichiometry of the salt part associated with, complex superstructures. The average structure is described in the orthorhombic space group Pmmm with a « 408 pm, b « 2263 pm, c « 849 pm. It feigns statistical distribution of vacancies and orientational disorder of the concatenated octahedra. By choosing the modulation vectors q₁ = 2/ta* + 1/2b* + 1/2c* with t ₁ = 13 or t₂ = 1.2, the additional weak. reflections of the diffraction, patterns are indexed. Ordered structure models are achieved in the [3+l]-dimensional superspace group Pmmm(α^{1/2 1/2})000 Metallic conductivity along [100], i. e. the direction of the ¹_∞[Pd@Bi_2/1Bi_8/2] ^2,5+ rods, was determined for a single-crystal. One-dimensional band structure calculations reveal. Bi p-bands crossing the Fermi level for formula charges higher than 2₊. The electron localization indicator (ELI) indicates two-center Bi-Bi bonds as well as multi-center bonds inside the metallic part, whereas the bismuth lone-pairs point towards the non-conducting part of the structure.