Jm. Harrowfield et al., LEWIS-BASE ADDUCTS OF LEAD(II) COMPOUNDS .7. SYNTHETIC AND STRUCTURALSTUDIES OF SOME 1 1 ADDUCTS OF LINEAR POLYAMINES WITH LEAD(II) NITRATE/, Australian Journal of Chemistry, 49(10), 1996, pp. 1029-1042
Syntheses and room-temperature single-crystal X-ray structure determin
ations are recorded for 1:1 adducts of lead(II) nitrate with the linea
r multidentate polyamines ethane-1,2-diamine ('en' (= '2')), H2N(CH2)(
2)NH(CH2)(2)NH2 ('dien' = '22') and H2N(CH2)(x)NH(CH2)(y)NH(CH2)(z)NH2
(zyztet = '222tet' (= 'trien'), '232tet', '323tet'). Crystal/refineme
nt data are as follows: [(en)Pb(NO3)(2)]((infinity/infinity)) is monoc
linic, P2(1)/c, a 5.388(2), b 12.440(5), c 13.123(3) Angstrom, beta 10
2.33(3)degrees, Z = 4 f.u.; R 0.037 for N-o 2698 'observed' (I > 3 sig
ma(I)) reflections. [(dien)Pb(NO3)(2)]((infinity/infinity)) is orthorh
ombic, Ccma, a 9.800(2), b 10.840(2), c 20.521(5), Z = 8; R 0.045, N-o
991. [(trien)Pb(NO3)(2)]((infinity/infinity)) is orthorhombic, P2(1)2
(1)2(1), a 14.815(3), b 10.975(3), c 8.410(2) Angstrom, Z = 4; R 0.050
, N-o 1360; [(232tet)Pb(NO3)(2)]((infinity/infinity)) is isomorphous,
a 14.524(6), b 11.221(1), c 8.860(2) Angstrom, R 0.036, N-o 2371. [(32
3tet)Pb(NO3)(2)]((infinity/infinity)) is monoclinic, P2(1)/c, a 8.195(
4), b 14.407(7), c 13.312(4) Angstrom, beta 91.05(3)degrees, Z = 4; R
0.049: N-o 1644. In general, the degree of complexity of the adduct di
minishes as the ligand size increases: whereas the en adduct is a comp
act one-dimensional two-stranded polymer with nearly all nitrate oxyge
ns involved in tight bridging interactions, the extent of bridging dim
inishes in the adducts of the larger amines, until, for the 323tet spe
cies, a monomer is obtained involving a lead coordination sphere conta
ining the ligand and a pair of bidentate nitrate groups. The 1:2 adduc
t with en is also recorded, and is a dimer with quasi-i internal symme
try. [(en)(2)Pb(NO3)(2)](2) is monoclinic, P2(1), a 6.661(2), b 14.226
(8), c 13.618(4) Angstrom, beta 96.51(2)degrees; R 0.072, N-o 1713.