Superspace description of the modulated structure of the metal-salt-hybrid Bi7 − δNi2Br5 − 2δ (δ = 1/9)
The compound Bi7 − δNi2Br5 − 2δ = (Bi3Ni)2[Bi1 − δBr4]Br1 −2δ (δ = 1/9) is a sub-bromide of the intermetallic phase Bi3Ni. Its crystal structure contains metallic rods, ^1_{\infty}[Bi3Ni], which are embedded in a salt-like matrix of bromido-bismuthate(III) and bromide anions. The non-stoichiometry originates from the variation of the number n of trans edge-sharing octahedra in the [Bi n Br4n + 2](n + 2)− oligomers (3 ≤ n ≤ 5), as well as from vacancies on the sites of the isolated Br atoms. The simplified structure is described in the orthorhombic space group Cmcm with a = 4.0660 (4), b = 23.305 (3), c = 17.130 (2) Å. It shows a statistical distribution of vacancies and orientational disorder of the concatenated octahedra. By choosing the modulation vector q = a*/9 + b*/2, the additional weak reflections of the diffraction pattern can be indexed. In the [3 + 1]-dimensional superspace group Pmnm(α½0)000, an ordered structure model is achieved. The modulated crystal structure bears a strong resemblance to the somewhat higher oxidized sub-bromide Bi7 − δNi2Br5 (δ = 1/9).