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-Phenan- throlinium) 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)(phenH2)(H2O)2] [BiCl6]’ is triclinic, P -1, a 9·791(1), b 9·338(3), c 8·311(3) Å, a 73·46(3), ß 69·71(2), ? 86·36(2)°, Z = 1; conventional R on | F | was 0·027 for N o 4852 independent ‘observed’ ( I > 3s( 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 ‘[(phenH2)(H2O)][BiCl5](8|8)’, monoclinic, P 2/ c , a 8·388(1), b 12·004(1), c 17·146(3) Å, ß 98·26(1)°, 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. [bpyH2]4 [Bi4Cl20] is monoclinic, P 21/ c , a 14·228(4), b 14·217(2), c 16·254(4) Å, ß 110·14(2)°, 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 a 19·288(7), b 14·251(3), c 7·644(3) Å, a 75·02(2), ß 80·15(3), ? 72·76(2)°, 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(µ-Cl)3BiCl3]3-. [phenH] [BiCl4](8|8),H2O is triclinic, space group P -1, a 12·119(7), b 10·169(6), c 7·247(4) Å, a 69·30(4), ß 75·05(4), ? 77·92(5)°, 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, P 21/ n , a 13·426(4), b 14·396(6), c 14·539(5) Å, ß 101·31(3)°, Z = 2, R 0·11 for N o 1862; the anion is of the form [I4Bi(µ-I)2BiI4]4- with quasi-octahedral bismuth. [bpyH] [BiI4](8|8) is monoclinic, C 2/ c , a 12·442(5), b 18·41(2), c 7·714(2) Å, ß 92·80(3)°, Z = 4, R 0·080 for N o 850, with a polymeric one-dimensional anion comparable to that in [phenH] [BiCl4](8|8),H2O. The structure of the 2,6-dimethylpyridinium salt of [BiCl6]3- is also recorded, as its acetonitrile solvate; triclinic, P -1, a 15·025(2), b 10·357(3), c 9·964(1) Å, a 83·14(2), ß 89·32(1), ? 86·61(2)°, 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) Å, ß 121·31(3)°, Z = 2, R 0·050 for N o 1379. Bands in the far-infrared and Raman spectra due to the v (BiCl) modes are assigned in [(phenH)(phenH2)(H2O)2] [BiCl6] and [bpyH2]4 [Bi4Cl20], and are discussed in relation to the structures of the complexes.