Structural systematics of rare earth complexes. XIX (Hydrated) 1 : 2 mononuclear adducts of lanthanoid(III) chlorides with 2,2 '-bipyridine and 1,10-phenanthroline

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 wat er, methanol or ethanol solutions, containing mononuclear arrays with 1 : 2 Ln/bpy or phen stoichiometry. LaCl3/phen/H2O(1 : 3 : 9), [(phen)(2)La(OH2) (5)]Cl-3.phen.4H(2)O, although of overall 1 : 3 LaCl3/phen stoichiometry, h as a lattice phen; it is orthorhombic, Pnna, a 19.947(7), b 16.457(5), c 12 .213(2) Angstrom, Z = 4; conventional R on \F\ was 0.030 for N-o 2567 'obse rved' (I >3 sigma(I)) diffractometer reflections. LaCl3/phen/H2O/MeOH (1 : 2 : 6 : 1), [(phen)(2)La(OH2)(5)]Cl-3.H2O.MeOH, is triclinic, <P(1)over bar >, a 19.060(3), b 9.252(3), c 8.994(3) Angstrom, alpha 69.33(3), beta 86.81 (2), gamma 89.66(2)degrees, Z = 2, R 0.037 for N-o 5452. LaCl3/bpy/H2O (1 : 2 : 6), [(bpy)(2)La(OH2)(4)Cl]Cl-2.2H(2)O, is monoclinic, P 2(1)/c, a 19.3 89(3), b 9.071(1), c 16.873(2) Angstrom, beta 114.10(1)degrees, Z = 4, R 0. 029 for N-o 4699. All three of these complexes have a nine-coordinate [(N,N '-bidentate)(2)La(unidentate)(5)] coordination environment with quasi-2 sym metry; that of the remaining compounds following is eight-coordinate [(N,N' -bidentate)(2)Ln(unidentate)(4)]. LuCl3/phen/H2O (1 : 2 : 6), [(phen)(2)Lu( OH2)(4)]Cl-3.2H(2)O, is monoclinic, C 2/c, a 11.045(7), b 17.660(6), c 14.4 74(9) Angstrom, beta 92.82(5)degrees, Z = 4, R 0.042 for N-o 1695, the Lu l ying on a crystallographic 2-axis. Crystals of LnCl(3)/phen/H2O (1 : 2 : 4) , [(phen)(2)Ln(OH2)(3)Cl]Cl-2.H2O (Ln = Dy, Er, Y), are triclinic, <P(1)ove r bar>, a approximate to 12.6, b approximate to 10.5, c approximate to 10.4 Angstrom, alpha approximate to 93.3, beta approximate to 109.3, gamma appr oximate to 96.8 degrees, Z = 2, R 0.030, 0.040, 0.052 for N-o 4221, 5100, 2 690 respectively. PrCl3/bpy/H2O/EtOH (1 : 2 : 1 : 0.5), [(bpy)(2)Pr(OH2)Cl- 3].1/2 EtOH, is triclinic, <P(1)over bar>, a 13.331(3), b 10.734(2), c 9.75 8(2) Angstrom, alpha 63.67(2), beta 78.99(2), gamma 71.24(2)degrees, Z = 2, R 0.033 for N-o 4596, while [(bpy)(2)Pr(OH2)(2)Cl-2]Cl is monoclinic, C 2/ c, a 15.921(15), b 11.314(8), c 14.114(8) Angstrom, beta 116.70(6)degrees, Z = 4, R 0.041 for N-o 2269. ErCl3/bpy/H2O(1 : 2 : 2 (also)), [(bpy)(2)Er(O H2)(2)Cl-2]Cl, is cubic, I 23, a 26.032(4) Angstrom, Z = 24, R 0.066 for N- o 1644. Crystals of LnCl(3)/phen/H2O/MeOH (1 : 2 : 1 : 1), [(phen)(2)Ln(OH2 )Cl-3].MeOH (Ln = La, Pr, Nd, Eu), are monoclinic, P 2(1)/a, a approximate to 13.2, b approximate to 10.7, c approximate to 18.5 Angstrom, beta approx imate to 102.1 degrees, Z = 4, R 0.054, 0.032, 0.040, 0.054 for N-o 2872, 4 792, 3179, 2847 respectively. LnCl(3)/bpy/H2O/EtOH (1 : 2 : 1 : 1), [(bpy)( 2)Ln(OH2)Cl-3].EtOH (Ln = Nd, Eu), are triclinic, <P(1)over bar>, a approxi mate to 11 3, b approximate to 10 9, c approximate to 10.4 Angstrom, alpha approximate to 75 5, beta approximate to 89. 8, gamma approximate to 78.0 degrees, Z = 2, R 0.044, 0.056 for N-o 4979, 3 596 respectively. LaCl3/bpy/EtOH (1 : 2 : 0 5) is binuclear [(bpy)(2)Cl2La( mu-Cl)(2)LaCl2(bpy)(2)].EtOH, monoclinic, P 2(1)/c, a 9.6878(2), b 17.5696( 3), c 16.1341(2) Angstrom, beta 123.10(1)degrees, Z = 2, R 0.033 for N-o 42 56. A totally unsolvated array is found for YbCl3/bpy (1 : 2), [(bpy)(2)YbC l3], monoclinic, P 2(1)/c, a 15.065(8), b 8.598(4), c 16.92(1) Angstrom, be ta 112.46(5)degrees, Z = 4, R 0.032 for N-o 3548, in which, alone, the meta l atom is seven-coordinate.