
%0 Journal Article
%A Bowmaker, Graham A. 
%A Harrowfield, Jack M. 
%A Junk, Peter C. 
%A Skelton, Brian W. 
%A White, Allan H. 
%T Syntheses, Structures and Vibrational Spectra of Some Dimethyl Sulfoxide Solvates of Bismuth(III) Bromide and Iodide
%J Australian Journal of Chemistry
%D 1998/04/17
%V 51
%N 4
%P 285-292
%K 
%R https://doi.org/10.1071/C97035
%U https://www.publish.csiro.au/paper/C97035 
%X Room-temperature single-crystal X-ray studies are recorded for some dimethyl sulfoxide (dmso) solvates of bismuth(III) bromide and iodide. Colourless BiBr3.3dmso is triclinic, P-1, a 8&#183;467(4), b 9&#183;109(4), c 13&#183;901(4) &#197;, &#945; 76&#183;34(4), &#946; 76&#183;95(4), &#947; 64&#183;56(4)&#176;, Z = 2; conventional R on &#124;F&#124; was 0&#183;050 for No 2306 independent &#8216;observed&#8217; (I &#62; 3&#963;(I)) reflections. The complex is mononuclear with a quasi-octahedral fac-bismuth environment, &#91;(dmso-O)3BiBr3&#93;, isomorphous with the previously determined chloride. Orange BiI3-2dmso is triclinic, P-1, a 12&#183;558(2), b 8&#183;962(2), c 8&#183;342(1) &#197;, &#945; 61&#183;85(1), &#946; 78&#183;27(1), &#947; 76&#183;89(2)&#176;, Z = 2 f.u., R 0&#183;048 for No 1953. The complex is binuclear, a pair of iodide atoms bridging the two bismuth atoms, &#91;(dmso-O)2I2Bi(&#181;-I)2BiI2(O-dmso)2&#93;; the two O-dmso ligands about each six-coordinate bismuth lie trans. Red BiI3.2 &frac23; dmso is triclinic, P-1, a 16&#183;435(6), b 14&#183;926(2), c 12&#183;396(3) &#197;, &#945; 74&#183;89(2), &#946; 73&#183;24(2), &#947; 79&#183;18(2)&#176;, Z = 6, R 0&#183;059 for No 5858. The complex is &#91;Bi(O-dmso)8&#93; &#91;Bi2I9&#93;, the eight-coordinate metal environment of the cation being, unusually, dodecahedral; in the anion a pair of quasi-octahedral six-coordinate bismuth atoms are bridged by three iodides, &#91;I3Bi(&#181;-I)3BiI3&#93;3-. Bands in the far-infrared and Raman spectra due to the v(BiX) modes are assigned and discussed in relation to the structures of the complexes. The assignment of the v(BiO) modes is discussed. 
