SYNTHETIC, STRUCTURAL AND VIBRATIONAL SPECTROSCOPIC STUDIES IN BISMUTH(III) HALIDE N,N'-AROMATIC BIDENTATE BASE SYSTEMS - 1 - LARGE-CATION (2,2'-BIPYRIDINIUM AND 1,10-PHENANTHROLINIUM) SALTS OF POLYHALOBISMUTHATE(III) IONS

Syntheses and room-temperature single-crystal X-ray studies are record ed for a variety of salts of cations derived from protonated 2,2'-bipy ridine and 1,10-phenanthroline (bpyH(+) and phenH(+)) with polyhalobis muthate(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 7 3.46(3), beta 69.71(2), gamma 86.36(2)degrees, Z = 1; conventional R o n \F\ was 0.027 for N-o 4852 independent 'observed' (I > 3 sigma(I)) r eflections. [BiCl6](3-) is closely octahedral, accompanied by an inter esting protonation/hydrogen-bonding array among the other moieties. Th e latter comment applies also to '[(phenH(2))(H2O)][BiCl5]((infinity/i nfinity))', monoclinic, P 2/c, a 8.388(1), b 12.004(1), c 17.146(3) An gstrom, beta 98.26(1)degrees, Z = 4, R 0.047 for N-o 2670, the anion a rray being a one-dimensional polymer with bridging chlorine atoms occu pying cis sites in the pseudo-octahedral coordination sphere of the bi smuth. [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 f or N-o 2777; in the novel centrosymmetric tetramer, the four bismuth a toms are bridged into a square array by four linearly coordinated halo gen atoms at the centres of the edges, a pair of these lying cis in th e pseudo-octahedral coordination sphere of each bismuth. [bpyH](3)[Bi2 Cl9] 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 bismu th atoms being bridged by three chlorine atoms on a mutual octahedral face, (3)BiCl3](3-).[phenH][BiCl4]((infinity/infinity)). H2O is tricli nic, 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, success ive metal atoms being bridged by pairs of chlorine atoms lying cis in the pseudo-octahedral coordination sphere. [bpyH](4)[Bi2I10] is monocl inic, P2(1)/n, a 13.426(4), b 14.396(6), c 14.539(5) Angstrom, beta 10 1.31(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]((i nfinity/infinity)) is monoclinic, C2/c, a 12.442(5), b 18.41(2), c 7.7 14(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), ga mma 86.61(2)degrees, Z = 2, R 0.046 for N-o 3601; there is also an iso morphous bromide, and also an isostoichiometric bromide modelled as mo noclinic, 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)(p henH(2))(H2O)(2)][BiCl6] and [bpyH(2)](4) [Bi4Cl20], and are discussed in relation to the structures of the complexes.