Understanding distortions of inorganic substructures in chloridobismuthates(III)

Abstract

The molar ratio variations of organic and inorganic reactants of chloridobismuthates(III) with N,N-dimethylethane-1,2-diammonium, [(CH3)2NH(CH2)2NH3]2+, and N,N,N′,N′-tetramethylguanidinium, [NH2C{N(CH3)2}2]+, cations lead to the formation of four different products, namely, tris(N,N-dimethylethane-1,2-diammonium) bis[hexachloridobismuthate(III)], [(CH3)2NH(CH2)2NH3]3[BiCl6]2 (1), catena-poly[N,N-dimethylethane-1,2-diammonium [[tetrachloridobismuthate(III)]-μ-chlorido]], {[(CH3)2NH(CH2)2NH3][BiCl5]} n (2), tris(N,N,N′,N′-tetramethylguanidinium) tri-μ-chlorido-bis[trichloridobismuthate(III)], [NH2C{N(CH3)2}2]3[Bi2Cl9] (3), and catena-poly[N,N,N′,N′-tetramethylguanidinium [[dichloridobismuthate(III)]-di-μ-chlorido]], {[NH2C{N(CH3)2}2][BiCl4]} n (4). The hybrid crystals 1–4, containing relatively large but different organic cations, are composed of four distinct anionic substructures. They are built up from isolated [BiCl6]3− octahedra in 1, from face-sharing bioctahedral [Bi2Cl9]3− units in 3, from polymeric corner-sharing {[BiCl5]2−} n chains in 2 and from edge-sharing {[BiCl4]−} n chains in 4. The distortions shown by the single [BiCl6]3− polyhedra in 1–4 are associated with intrinsic interactions within the anionic substructures and the organic...inorganic substructures interactions, namely, N/C—H...Cl hydrogen bonds. The first factor is the stronger, which is evident in comparison of the experimentally determined geometrical and calculated distortion parameters for the isolated octahedron in 1 to the more complex inorganic substructures in 2–4. The formation of N—H...Cl hydrogen bonds, in terms of their number and strength, is favoured for 1 and 3 containing relatively easily accessed hydrogen-bond acceptors of isolated [BiCl6]3− and [Bi2Cl9]3− units. The studies of the deviations from regularity of the [BiCl6]3− octahedra within inorganic substructures were supported by a survey of the Cambridge Structural Database, which confirmed the role played by different factors in the variations in geometry of the inorganic anions.

The structural versatility of proton sponge bismuth halides

“…One may however note that the bridging chlorides are far from being symmetrically linked to the adjacent Bi ions (2.71 and 2.73 Å for the shortest distances, and 2.96 and 2.99 Å for the longest ones). These unexpected observation finds a strong confirmation in the crystal structures of known analogues, [34][35][36][37] where shorter (avg. 2.73 Å) and longer (avg.…”

Reaction of bis(dialkylphosphino)amines R2PNHPR2 (R = i-Pr, t-Bu, Ph) with halogens X2 (X = Cl, Br, I): different solvents – different stories

“…Halobismuthates with the empirical formula BiCl 4 can range in size from mononuclear discrete anions to polymeric chains and more complex networks. 29,30 The bismuth product characterized here shows that there is yet another mode of reactivity for bis(dialkylphosphino)amines in this system. Instead of forming any sort of coordination complex with bismuth, an asymmetric bismuth chloride trimer of the monoanion [BiCl 4 ] − has crystallized.…”