Structural Systematics of Rare Earth Complexes. XII Solvated 1 : 1 Adducts of Some Lanthanoid( <i>III</i> ) Carboxylates with 1,10-Phenanthroline and 2,2′:6′,2&amp;Prime;-Terpyridine

Abstract

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, a 12·430(8), b 10·681(4), c 8·134(8) Å, a 74·76(6), ß 84·81(7), ? 74·29(4)°, Z = 2 f.u.; conventional R on | F | was 0·031 for N o 3939 independent ‘observed’ ( I &amp;gt; 3s( I )) diffractometer reflections. The complex [( N , N '-phen)( O , O '-ac)Lu( O -ac- O ')4Lu( O , O '-ac)( N , N '-phen)].2H2O is binuclear, the lutetium being eight-coordinated by bidentate phen and ac (acetate) ligands and four oxygen atoms from the bridging acetate ligands. Also recorded is the structural characterization of 1 : 1 Lu(ac)2Cl/tpy (tpy = 2,2':6',2"-terpyridine) as its pentahydrate; this complex is triclinic, P 1, a 12·410(3), b 11·559(4), c 9·976(4) Å, a 85·19(3), ß 70·30(3), ? 65·70(2)°, Z = 2, R 0·049 for N o 4717. The complex is shown to be [(tpy)(H2O)2Lu(O2CCH3)2]Cl.3H2O, with the lutetium nine-coordinated by tridentate tpy, a pair of bidentate acetates and two unidentate water molecules, with the chloride uncoordinated. Structural characterizations of a number of 1 : 1 adducts of variously solvated lanthanoid(III) trichloroacetates, Ln(tca)3, with tpy are also recorded. Yb(tca)3/tpy/MeOH (1 : 1 : 1) is triclinic, P 1, a 14·016(4), b 12·951(5), c 9·604(3) Å, a 73·89(3), ß 76·56(3), ? 69·20(3)°, Z = 2 f.u., R 0·057 for N o 4465. The complex is mononuclear, the eight-coordinate N3YbO5 array containing tridentate tpy, unidentate 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, a ˜ 13·4, b ˜ 12·47, c ˜ 11·5 Å, a ˜ 114·5, ß ˜ 89·9, ? ˜ 115·6°, Z = 1 binuclear array, R 0·061, 0·071 for N o 3240, 2394. The two Ln atoms are O , O '-bridged by a pair of anions, the N3LnO6 nine-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, a 16·569(8), b 14·815(5), c 14·375(6) Å, a 62·05(3), ß 81·35(4), ? 77·97(3)°, Z = 4 ‘mononuclear’ f.u., R 0·067 for N o 6710. The array, remarkably, contains species of both of the above types in a 1 : 2 binuclear-to-mononuclear ratio, but with water replacing methanol in the mononuclear array.