Bidentate Nitrogen Base Adducts of Bismuth(III) Nitrate

Abstract

Syntheses and single-crystal X-ray structure determinations are reported for a number of adducts of bismuth(III) nitrate with the aromatic bidentate base systems 2,2′-bipyridine (bpy) or 1,10-phenanthroline (phen). With bpy, a mononuclear 1 : 2 adduct is formed, [(bpy)₂Bi(O₂NO)₃], isomorphous with its rare earth counterparts, orthorhombic, Pbcn, a 16·7634(8), b 8·9970(4), c 15·0099(7) Å, Z = 4, conventional R on |F| 0·029 for N_o 2502 independent ‘observed’ reflections. The Bi centre is 10-coordinate with two bidentate N-base ligands and three bidentate nitrate ligands. With phen the 10-coordinate 1 : 2 adduct [(phen)₂Bi(O₂NO)₃] was readily obtained, while the 1 : 1 adduct proved elusive and a hydroxide-bridged dimer [(phen)(ONO₂)₂Bi(µ-OH)₂Bi(O₂NO)₂(phen)] with eight-coordinate Bi centres was the sole product from all crystallization attempts. [(phen)₂Bi(O₂NO₃)₃] is monoclinic, C2/c, a 11·258(5), b 17·847(4), c 13·044(5) Å, β 100·78(4)°, Z = 4, R 0·063 for N_o 1958, again isomorphous with its rare earth counterparts; [(phen)(ONO₂)₂Bi(µ-OH)₂Bi(O₂NO)₂(phen)] is triclinic, P^-1, a 8·3251(6), b 8·6315(6), c 10·7650(8) Å, α 111·120(1), β 93·486(1), γ 102·364(1)°, Z = 1, dimer, R 0·024 for N_o 2965. In all syntheses, dimethyl sulfoxide (dmso) was used as the supporting solvent; the structure determination of the dmso adduct [(dmso-O)₃Bi(O₂NO)₃] is also recorded where the Bi centre is nine-coordinate with three bidentate nitrate ligands and three O-bound dmso ligands: monoclinic P2₁/n, a 11·4136(6), b 12·6682(7), c 13·4959(7) Å, β 100·209(1)°, Z = 4, R 0·026 for N_o 4214.