
%0 Journal Article
%A Bowmaker, Graham A. 
%A Junk, Peter C. 
%A Lee, Aaron M. 
%A Skelton, Brian W. 
%A White, Allan H. 
%T Synthetic, Structural and Vibrational Spectroscopic Studies in Bismuth(III) Halide/<emph type="2">N,N</emph>&#x2032;-Aromatic Bidentate Base Systems. I Large-Cation (2,2&#x2032;-Bipyridinium and 1,10-Phenan- throlinium) Salts of Polyhalobismuthate(III) Ions
%J Australian Journal of Chemistry
%D 1998/04/17
%V 51
%N 4
%P 293-309
%K 
%R https://doi.org/10.1071/C97036
%U https://www.publish.csiro.au/paper/C97036 
%X Syntheses and room-temperature single-crystal X-ray studies are recorded for a variety of salts of cations derived from protonated 2,2&#8242;-bipyridine and 1,10-phenanthroline (bpyH+ and phenH+) with polyhalobismuthate(III) anions. &#8216;&#91;(phenH)(phenH2)(H2O)2&#93; &#91;BiCl6&#93;&#8217; is triclinic, P-1, a 9&#183;791(1), b 9&#183;338(3), c 8&#183;311(3) &#197;, &#945; 73&#183;46(3), &#946; 69&#183;71(2), &#947; 86&#183;36(2)&#176;, Z = 1; conventional R on &#124;F&#124; was 0&#183;027 for No 4852 independent &#8216;observed&#8217; (I &#62; 3&#963;(I)) reflections. &#91;BiCl6&#93;3- is closely octahedral, accompanied by an interesting protonation/hydrogen-bonding array among the other moieties. The latter comment applies also to &#8216;&#91;(phenH2)(H2O)&#93;&#91;BiCl5&#93;(&infin;|&infin;)&#8217;, monoclinic, P2/c, a 8&#183;388(1), b 12&#183;004(1), c 17&#183;146(3) &#197;, &#946; 98&#183;26(1)&#176;, Z = 4, R 0&#183;047 for No 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. &#91;bpyH2&#93;4 &#91;Bi4Cl20&#93; is monoclinic, P21/c, a 14&#183;228(4), b 14&#183;217(2), c 16&#183;254(4) &#197;, &#946; 110&#183;14(2)&#176;, Z = 2, R 0&#183;045 for No 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. &#91;bpyH&#93;3 &#91;Bi2Cl9&#93; is triclinic, P-1 a 19&#183;288(7), b 14&#183;251(3), c 7&#183;644(3) &#197;, &#945; 75&#183;02(2), &#946; 80&#183;15(3), &#947; 72&#183;76(2)&#176;, Z = 2, R 0&#183;072 for No 3600, the two pseudo-octahedrally coordinated bismuth atoms being bridged by three chlorine atoms on a mutual octahedral face, &#91;Cl3Bi(&#181;-Cl)3BiCl3&#93;3-. &#91;phenH&#93; &#91;BiCl4&#93;(&infin;|&infin;),H2O is triclinic, space group P-1, a 12&#183;119(7), b 10&#183;169(6), c 7&#183;247(4) &#197;, &#945; 69&#183;30(4), &#946; 75&#183;05(4), &#947; 77&#183;92(5)&#176;, Z = 2, R 0&#183;035 for No 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. &#91;bpyH&#93;4 &#91;Bi2I10&#93; is monoclinic, P21/n, a 13&#183;426(4), b 14&#183;396(6), c 14&#183;539(5) &#197;, &#946; 101&#183;31(3)&#176;, Z = 2, R 0&#183;11 for No 1862; the anion is of the form &#91;I4Bi(&#181;-I)2BiI4&#93;4- with quasi-octahedral bismuth. &#91;bpyH&#93; &#91;BiI4&#93;(&infin;|&infin;) is monoclinic, C2/c, a 12&#183;442(5), b 18&#183;41(2), c 7&#183;714(2) &#197;, &#946; 92&#183;80(3)&#176;, Z = 4, R 0&#183;080 for No 850, with a polymeric one-dimensional anion comparable to that in &#91;phenH&#93; &#91;BiCl4&#93;(&infin;|&infin;),H2O. The structure of the 2,6-dimethylpyridinium salt of &#91;BiCl6&#93;3- is also recorded, as its acetonitrile solvate; triclinic, P-1, a 15&#183;025(2), b 10&#183;357(3), c 9&#183;964(1) &#197;, &#945; 83&#183;14(2), &#946; 89&#183;32(1), &#947; 86&#183;61(2)&#176;, Z = 2, R 0&#183;046 for No 3601; there is also an isomorphous bromide, and also an isostoichiometric bromide modelled as monoclinic, Cm, a 18&#183;128(6), b 10&#183;348(2), c 10&#183;241(2) &#197;, &#946; 121&#183;31(3)&#176;, Z = 2, R 0&#183;050 for No 1379. Bands in the far-infrared and Raman spectra due to the v(BiCl) modes are assigned in &#91;(phenH)(phenH2)(H2O)2&#93; &#91;BiCl6&#93; and &#91;bpyH2&#93;4 &#91;Bi4Cl20&#93;, and are discussed in relation to the structures of the complexes. 
