Structural systematics of rare earth complexes. XII - Solvated 1 : 1 adducts of some lanthanoid(III) carboxylates with 1,10-phenanthroline and 2,2 ':6 ',20 ''-terpyridine
Cj. Kepert et al., Structural systematics of rare earth complexes. XII - Solvated 1 : 1 adducts of some lanthanoid(III) carboxylates with 1,10-phenanthroline and 2,2 ':6 ',20 ''-terpyridine, AUST J CHEM, 52(6), 1999, pp. 481-496
A room-temperature single-crystal X-ray structure determination of the 1 :
1 adduct of 1,10-phenanthroline ('phen') with lutetium(III) acetate (as its
dihydrate) is recorded. Crystals are triclinic, <P(1)over bar>, a 12.430(8
), b 10.681(4), c 8.134(8) Angstrom, alpha 74.76(6), beta 84.81(7), gamma 7
4.29(4)degrees, Z = 2 f.u.; conventional R on \F\ was 0.031 for N-o 3939 in
dependent 'observed' (I > 3 sigma(I)) diffractometer reflections. The compl
ex [(N,N'-phen)(O,O'-ac)Lu(O-ac-O')(4)Lu(O,O'-ac)(N,N'-phen)].2H(2)O is bin
uclear, the lutetium being eight-coordinated by bidentate phen and ac (acet
ate) ligands and four oxygen atoms from the bridging acetate ligands. Also
recorded is the structural characterization of 1 : 1 Lu(ac)(2)Cl/tpy (tpy =
2,2':6',2 "-terpyridine) as its pentahydrate; this complex is triclinic, <
P(1)over bar>, a 12.410(3), b 11.559(4), c 9.976(4) Angstrom, alpha 85.19(3
), beta 70.30(3), gamma 65.70(2)degrees, Z = 2, R 0.049 for N-o 4717. The c
omplex is shown to be [(tpy)(H2O)(2)Lu(O2CCH3)(2)]Cl.3H(2)O, with the lutet
ium nine-coordinated by tridentate tpy, a pair of bidentate acetates and tw
o unidentate water molecules, with the chloride uncoordinated.
Structural characterizations of a number of 1 : 1 adducts of variously solv
ated lanthanoid(III) trichloroacetates, Ln(tca)(3), with tpy are also recor
ded. Yb(tca)(3)/tpy/MeOH (1 : 1 : 1) is triclinic, <P(1)over bar>, a 14.016
(4), b 12.951(5), c 9.604(3) Angstrom, alpha 73.89(3), beta 76.56(3), gamma
69.20(3)degrees, Z = 2 f.u., R 0.057 for N-o 4465. The complex is mononucl
ear, the eight-coordinate N3YbO5 array containing tridentate tpy, unidentat
e methanol, and two unidentate and one bidentate chelating anions. 1 : 1 :
1 Ln(tca)(3)/tpy/OH2 adducts for Ln = La(-)Nd are triclinic, <P(1)over bar>
, a approximate to 13.4, b approximate to 12.47, c approximate to 11.5 Angs
trom, alpha approximate to 114.5, beta approximate to 89.9, gamma approxima
te to 115.6 degrees, Z = 1 binuclear array, R 0.061, 0.071 for N-o 3240, 23
94. The two Ln atoms are O,O'-bridged by a pair of anions, the N(3)LnO(6) n
ine-coordinate lanthanoid environment being completed by a tridentate tpy,
one water, one unidentate and one bidentate anion. A 1 : 1 : 1 Lu(tca)3/tpy
/OH2 array, by contrast, is triclinic, <P(1)over bar>, a 16.569(8), b 14.81
5(5), c 14.375(6) Angstrom, alpha 62.05(3), beta 81.35(4), gamma 77.97(3)de
grees, Z = 4 'mononuclear' f.u., R 0.067 for N-o 6710. The array, remarkabl
y, contains species of both of the above types in a 1 : 2 binuclear-to-mono
nuclear ratio, but with water replacing methanol in the mononuclear array.