Anionic Diversity in Iodobismuthate Chemistry

Three salts containing different iodobismuthate anions have been synthesized. [(CH 3 ) 2 NH 2 ] 3 [BiI 6 ] was prepared by oxidation of bismuth by iodine in N,N ‐dimethylformamide. [(CH 3 ) 2 NH 2 ] 3 [BiI 6 ] crystallizes in the space group ${\rm R}{\bar 3}$ with a = 30.760(3) Å and c = 8.8039(5) Å and contains monomeric [BiI 6 ] 3− anions. The hydrate Na 4 [Bi 2 I 10 ] · 14H 2 O was prepared by the oxidation of bismuth using iodine in acetonitrile in the presence of NaI. Na 4 [Bi 2 I 10 ] · 14H 2 O crystallizes in the space group C 2/ m with a = 12.875(2) Å, b = 16.177(2) Å, c = 9.904(2) Å and β = 106.57(6)°. The structure contains dimeric [Bi 2 I 10 ] 4− anions and rows of sodium ions, with bridging water molecules. The hydrate [Na{(CH 3 ) 2 NCHO} 2 (H 2 O)] 3 [Bi 2 I 9 ] was prepared by dissolution of Na 4 [Bi 2 I 10 ] · 14H 2 O in N,N ‐dimethylformamide and crystallizes in the space group ${\rm P}{\bar 1}$ with a = 13.2309(13) Å, b = 13.3791(14) Å, c = 18.722(2) Å, α = 70.338(9)°, β = 72.651(9)° and γ = 62.183(5). The structure contains dimeric [Bi 2 I 9 ] 3− anions and cationic polymers,   ∞ 1 [Na{(CH 3 ) 2 NCHO} 2 (H 2 O)] + .