Synthetic, structural and vibrational spectroscopic studies in bismuth(III) halide N,N′-aromatic bidentate base systems.: I.: Large-cation (2,2′-bipyridinium and 1,10-phenanthrolinium) salts of polyhalobismuthate(III) ions

Syntheses and room-temperature single-crystal X-ray studies are recorded for a variety of salts of cations derived from protonated 2,2'-bipyridine and 1,10-phenanthroline (bpyH(+) and phenH(+)) with polyhalobismuthate(III) anions. '[(phenH)(phenH(2))(H2O)(2)][BiCl6]' is triclinic, <P(1)over bar>, a 9.791(1), b 9.338(3), c 8.311(3) Angstrom, alpha 73.46(3), beta 69.71(2), gamma 86.36(2)degrees, Z = 1; conventional R on \F\ was 0.027 for N-o 4852 independent 'observed' (I > 3 sigma(I)) reflections. [BiCl6](3-) is closely octahedral, accompanied by an interesting protonation/hydrogen-bonding array among the other moieties. The latter comment applies also to '[(phenH(2))(H2O)][BiCl5]((infinity/infinity))', monoclinic, P 2/c, a 8.388(1), b 12.004(1), c 17.146(3) Angstrom, beta 98.26(1)degrees, Z = 4, R 0.047 for N-o 2670, the anion array being a one-dimensional polymer with bridging chlorine atoms occupying cis sites in the pseudo-octahedral coordination sphere of the bismuth. [bpyH(2)](4)[Bi4Cl20] is monoclinic, P2(1)/c, a 14.228(4), b 14.217(2), c 16.254(4) Angstrom, beta 110.14(2)degrees, Z = 2, R 0.045 for N-o 2777; in the novel centrosymmetric tetramer, the four bismuth atoms are bridged into a square array by four linearly coordinated halogen atoms at the centres of the edges, a pair of these lying cis in the pseudo-octahedral coordination sphere of each bismuth. [bpyH](3)[Bi2Cl9] is triclinic, <P(1)over bar>, a 19.288(7), b 14.251(3), c 7.644(3) Angstrom, alpha 75.02(2), beta 80.15(3), gamma 72.76(2)degrees, Z = 2, R 0.072 for N-o 3600, the two pseudo-octahedrally coordinated bismuth atoms being bridged by three chlorine atoms on a mutual octahedral face, [Cl3Bi(mu-Cl)(3)BiCl3](3-).[phenH][BiCl4]((infinity/infinity)). H2O is triclinic, space group <P(1)over bar>, a 12.119(7), b 10.169(6), c 7.247(4) Angstrom, alpha 69.30(4), beta 75.05(4), gamma 77.92(5)degrees, Z = 2, R 0.035 for N-o 2348. The anion is a one-dimensional polymer, successive metal atoms being bridged by pairs of chlorine atoms lying cis in the pseudo-octahedral coordination sphere. [bpyH](4)[Bi2I10] is monoclinic, P2(1)/n, a 13.426(4), b 14.396(6), c 14.539(5) Angstrom, beta 101.31(3)degrees, Z = 2, R 0.11 for N-o 1862; the anion is of the form [I4Bi(mu-I)(2)BiI4](4-) with quasi-octahedral bismuth. [bpyH] [BiI4]((infinity/infinity)) is monoclinic, C2/c, a 12.442(5), b 18.41(2), c 7.714(2) Angstrom, beta 92.80(3)degrees, Z = 4, R 0.080 for N-o 850, with a polymeric one-dimensional anion comparable to that in [phenH][BiCl4]((infinity/infinity)). H2O. The triclinic, <P(1)over bar>, a 15.025(2), b 10.357(3), c 9.964(1) Angstrom, alpha 83.14(2), beta 89.32(1), gamma 86.61(2)degrees, Z = 2, R 0.046 for N-o 3601; there is also an isomorphous bromide, and also an isostoichiometric bromide modelled as monoclinic, Cm, a 18.128(6), b 10.348(2), c 10.241(2) Angstrom, beta 121.31(3)degrees, Z = 2, R 0.050 for N-o 1379. Bands in the far-infrared and Raman spectra due to the nu(BiCl) modes are assigned in [(phenH)(phenH(2))(H2O)(2)][BiCl6] and [bpyH(2)](4) [Bi4Cl20], and are discussed in relation to the structures of the complexes.