
%0 Journal Article
%A Engelhardt, LM 
%A Harrowfield, JM 
%A Miyamae, H 
%A Patrick, JM 
%A Skelton, BW 
%A Soudi, AA 
%A White, AH 
%T Lewis-Base Adducts of Lead(II) Compounds. XVII. Synthetic and Structural Studies of Some 1:1 Adducts of 2,2':6,2'-Terpyridine With Lead(II) Salts
%J Australian Journal of Chemistry
%D 1996/10/01
%V 49
%N 10
%P 1135-1146
%K 
%R https://doi.org/10.1071/CH9961135
%U https://www.publish.csiro.au/paper/CH9961135 
%X Syntheses and room-temperature single-crystal X-ray structure determinations are recorded for 1:1 adducts of 2,2':6',2"-terpyridine (' tpy ') with the lead(II) oxoanion salts perchlorate, nitrate and nitrite, ( tpy ) Pb ( oxoanion )2. All structures are monoclinic, C2/c, Z = 4, with approximate ranges a from 9 to 11 &#506;, b from 16 to 20 &#506;, c from 9.8 to 13.8 &#506;, &#946; from 113 to 130&#176; and V from 1650 to 1850 &#506;3. In all cases the lead(II) atoms are disposed on crystallographic 2 axes which also pass through the axis of the central tpy ring; a pair of symmetry related oxoanions link successive lead atoms in a one-dimensional polymeric chain parallel to the ac cell diagonal, one pair of oxygen atoms functioning as an O,O'-bidentate with another oxygen (replaced by the nitrogen in the nitrite) bridging to the adjacent lead atom; the third anionic oxygen atom in the nitrate is replaced by a water molecule in the nitrite, which thus becomes a monohydrate. Residuals were 0.030, 0.034 and 0.040 for 2122, 1564 and 2059 independent 'observed' (I > 3&#963;(I)) reflections respectively. Also recorded are the syntheses and room-temperature single-crystal X-ray structure determinations for 1:1 aducts of 2,2':6',2"-terpyridine with lead(II) chloride, bromide and iodide, the chloride and bromide being hydrated. ( tpy )PbCl2.H2O is monoclinic, P 21/c, a 8.938(1), b 15,210(7), c 13.414(3) &#506;, &#946; 115.17(1)&#176;, Z = 4 f.u .; R was 0.036 for No = 3346 independent, 'observed' reflections. The complex is centrosymmetric, binuclear [( tpy ) (H2O)( Cl ) Pb (&#956;- Cl )2Pb( Cl )(OH2)( tpy )], with the two lead atoms linked by bridging chlorine atoms; the lead atoms are seven-coordinate N3,O,ClPb(&#956;- Cl )2. The bromide ( tpy )PbBr2.2/3H2O, triclinic, P&#299;, a 12.360(6), b 12.452(4), c 18.372(6) &#506;, &#945; 108.31(3), &#946; 109.44(3), &#947; 90.56(3)&#176;, Z = 6 f.u ., R being 0.046 for No 7282, is in fact trinuclear [Pb3Br6( tpy )6].2H2O, a novel and elegant oligomer with quasi-2 symmetry in which a central lead atom (on the quasi-2 axis) is seven-coordinated [( tpy ) Pb (&#956;-Br)4] with the associated bromides bridging to a pair of peripheral lead atoms, also seven coordinated, [( tpy )(Br) Pb (&#956;-Br)3]. Unsolvated ( tpy )PbI2, triclinic, P&#299; , a 10.834(3), b 9.023(3), c 8.906(2) &#506;, &#945; 80.34(2), &#946; 89.40(2), &#947; 79.78(2)&#176;, Z = 2 f.u ., R 0.031 for No 2347 is, like the chloride, centrosymmetric binuclear, [( tpy )(I) Pb (&#956;-I)2Pb(I)( tpy )], but with the lead(II) now six-coordinate N3(I) Pb (&#956;-I)2. In both chloride and iodide, the tpy plane is approximately normal to the Pb ... Pb line with the water molecule of the chloride approximately trans to the central tpy nitrogen; in the iodide that site is occupied by the terminal halide. 
