Synthesis, structure, and properties of Schiff base iodobismuthate and its alteration in DMSO solution

Abstract

New hybrid iodobismuthates (C₁₂H₁₈N₂)(BiI₄)₂ (1, C₁₂H₁₈N₂ is N,N´-bis(1- methylethylidene)-1,4-benzоdiammonium dication) and (C₆H₄(NH₃)₂) [Bi₂I₈•2DMSO]•4DMSO (2, C₆H₄(NH₃)₂ is p-phenylenediammonium dication) were synthesized and their crystal structures were established. Compound 1 crystallizes in the space group P2₁/n, a = 7.632(4), b = 13.471(6), c = 14.556(5) Å, β = 93.57(4)°; compound 2 crystallizes in the space group P\(\overline 1 \), a = 9.208(4), b = 12.203(5), c = 13.600(5) Å, α = 110.20(3)°, β = 97.28(4)°, γ = 110.04(4)°. In the crystal structure of compound 1, one-dimensional infinite BiI₄^– polyanions are linked into a three-dimensional structure by N,N'-bis(1-methylethylidene)- 1,4-benzоdiammonium dications through N–H…I and C–H…I hydrogen bonds. Compound 1 is stable up to 200 °С, optical studies showed that it has a band gap of 2.15 eV. The recrystallization of compound 1 from DMSO is accompanied by the transformation of chain BiI₄^–anions to binuclear [Bi₂I₈•2DMSO]^2– anions, while the azomethine cation decomposes to form a p-phenylenediammonium dication.