Structural Systematics of Rare Earth Complexes. XIX (Hydrated) 1 : 2 Mononuclear Adducts of Lanthanoid(III) Chlorides with 2,2′-Bipyridine and 1,10-Phenanthroline

Abstract

Room-temperature single-crystal X-ray structure determinations are recorded for a number of adducts of hydrated lanthanoid(III) trichlorides with 2,2′-bipyridine (‘bpy’) and 1,10-phenanthroline (‘phen’), crystallized from water, methanol or ethanol solutions, containing mononuclear arrays with 1 : 2 Ln/bpy or phen stoichiometry. LaCl₃/phen/H₂O(1 : 3 : 9), [(phen)₂La(OH₂)₅]Cl₃.phen.4H₂O, although of overall 1 : 3 LaCl₃/phen stoichiometry, has a lattice phen; it is orthorhombic, Pnna, a 19·947(7), b 16·457(5), c 12·213(2) Å, Z = 4; conventional R on |F| was 0·030 for N_o 2567 ‘observed’ (I >3σ(I)) diffractometer reflections. LaCl₃/phen/H₂O/MeOH (1 : 2 : 6 : 1), [(phen)₂La(OH₂)₅]Cl₃.H₂O.MeOH, is triclinic, P 1, a 19·060(3), b 9·252(3), c 8·994(3) Å, α 69·33(3), β 86·81(2), γ 89·66(2)°, Z = 2, R 0·037 for N_o 5452. LaCl₃/bpy/H₂O (1 : 2 : 6), [(bpy)₂La(OH₂)4Cl]Cl₂.2H₂O, is monoclinic, P 2₁/c, a 19·389(3), b 9·071(1), c 16·873(2) Å, β 114·10(1)°, Z = 4, R 0·029 for N_o 4699. All three of these complexes have a nine-coordinate [(N,N′-bidentate)₂La(unidentate)₅] coordination environment with quasi-2 symmetry; that of the remaining compounds following is eight-coordinate [(N,N′-bidentate)₂Ln(unidentate)₄]. LuCl₃/phen/H₂O (1 : 2 : 6), [(phen)₂Lu(OH₂)4]Cl₃.2H₂O, is monoclinic, C 2/c, a 11·045(7), b 17·660(6), c 14·474(9) Å, β 92·82(5)°, Z = 4, R 0·042 for N_o 1695, the Lu lying on a crystallographic 2 -axis. Crystals of LnCl3/phen/H₂O(1 : 2 : 4), [(phen)₂Ln(OH₂)₃Cl]Cl₂.H₂O (Ln = Dy, Er, Y), are triclinic, P 1, a≈ 12·6, b ≈ 10·5, c ≈ 10·4 Å, α ≈ 93·3, β ≈ 109·3, γ ≈ 96·8°, Z = 2, R 0·030, 0·040, 0·052 for No 4221, 5100, 2690 respectively. PrCl₃/bpy/H₂O/EtOH (1 : 2 : 1 : 0·5), [(bpy)₂Pr(OH₂)Cl₃].½EtOH, is triclinic, P 1, a 13·331(3), b 10·734(2), c 9·758(2) Å, α 63·67(2), β 78·99(2), γ 71·24(2)°, Z = 2, R 0·033 for N_o 4596, while [(bpy)₂Pr(OH₂)₂Cl₂]Cl is monoclinic, C 2/c, a 15·921(15), b 11·314(8), c 14·114(8) Å, β 116·70(6)°, Z = 4, R 0·041 for N_o 2269. ErCl₃/bpy/H₂O(1 : 2 : 2 (also)), [(bpy)₂Er(OH₂)₂Cl₂]Cl, is cubic, I 23, a 26·032(4) Å, Z = 24, R 0·066 for N_o 1644. Crystals of LnCl₃/phen/H₂O/MeOH (1 : 2 : 1 : 1), [(phen)₂Ln(OH₂)Cl₃].MeOH (Ln = La, Pr, Nd, Eu), are monoclinic, P 2₁/a, a ≈ 13·2, b ≈ 10·7, c ≈ 18·5 Å, β ≈ 102·1°, Z = 4, R 0·054, 0·032, 0·040, 0·054 for No 2872, 4792, 3179, 2847 respectively. LnCl₃/bpy/H₂O/EtOH (1 : 2 : 1 : 1), [(bpy)₂Ln(OH₂)Cl₃].EtOH (Ln = Nd, Eu), are triclinic, P 1, a ≈ 11·3, b ≈ 10·9, c ≈ 10·4 Å, α ≈ 75·5, β ≈ 89·8, γ ≈ 78·0°, Z = 2, R 0·044, 0·056 for N_o 4979, 3596 respectively. LaCl₃/bpy/EtOH (1 : 2 : 0·5) is binuclear [(bpy)₂Cl₂La(µ-Cl)₂LaCl₂(bpy)₂].EtOH, monoclinic, P 2₁/c, a 9·6878(2), b 17·5696(3), c 16·1341(2) Å, β 123·10(1)°, Z = 2, R 0·033 for N_o 4256. A totally unsolvated array is found for YbCl₃/bpy (1 : 2), [(bpy)₂YbCl₃], monoclinic, P 2₁/c, a 15·065(8), b 8·598(4), c 16·92(1) Å, β 112·46(5)°, Z = 4, R 0·032 for N_o 3548, in which, alone, the metal atom is seven-coordinate.